Thanks to Art_Izon for editing and helping out with this guide!

You will want to follow the guide in the order shown here. It is the best route for less menuing and the such. If you need visual references, the best thing to check would be the IL records for the missions in question.

Some things to learn before starting:

Byakuya: You'll want to learn to do the [ ] [ ] /\ loop. Its the fastest way to kill bosses. You'll need to learn the timing, since you can’t just spam it. I would start learning it on Mission 28 and practicing the timing there since there are plenty of bosses to fight to get the hang of it. His ult isn’t worth using.

Barragan : Another fantastic character, only let down by how slow his dash is and just how good the top 3 are. His ground O is extremely good. It deletes most if not all projectiles and ignores armor on the turtle Hollows. While in ignition his ground O is always active for free as long as Ignition persists. Also it’s active during the Ignition activation cutscene - if you’re next to an enemy and use Ignition they will be frozen in place for your animation and still take the damage. A good combo is to use your [ ] until they are launched in the air then use /\ /\ /. His ult is a good one and on the higher side damage-wise. As always I’ll recommend just testing the limits of its hit box to get a feel for it (it’s roughly cone-shaped) but not really needed since he is only used twice here and the two bosses in both are almost always together.

Harribel : Her aerial O is fantastic for bosses if done right - it can trap them in an infinite loop. Her / \ has a massive hitbox and good damage for its cost. This is the main use for her in NG+ Mission Mode since the 2 missions she’s in, she can clear the large amounts of mobs and fight the boss easily. Her ultimate is bad and like Byakuya’s, not worth using.

Yoruichi : She has the fastest ult in the game clocking in at about 6 seconds before you can move again. For the one mission you use her in just keep in mind her jumping O will glide you against a wall if your hitting it at an angle. just be careful to not use her ground O, it’s not very good and wastes a decent amount of both SP and time.

Grimmjow: His ground O, Gran Rey Cero, can shoot through walls if performed close enough to one. This, combined with its effectively infinite range, makes him the only practical choice for mission 12. You'll want to be either right against the wall or just barely away from it. His aerial O ( Desgarron ) is also fantastic, especially if you can wallbounce an enemy, or against an immobile target like Rudobon. In these situations, it will hit multiple times. His ult has poor range so keep close to the enemy before using it.

Final Form Ichigo : now lets talk about one of if not the best character for this game. his ult is the highest damaging ult in the game. While it’s the slowest, (about 15 seconds till you can move after using it) for missions with more then one boss it is much faster and safer to just use Mugetsu instead of praying they fall into your combo as Byakuya. The black slash that is shown is like only a 3rd of the size of the actual hit box, which is extremely large. Do not under any circumstance use ult as soon as you enter the boss rooms. because for some reason there will be a bit of invincibility frames for mugetsu on the bosses. Luckily, however, the Ignition cutscene lets the game continue going in the back ground while freezing ALL mobs in place, so this allows you to save your Ignition until you enter. Activate it and use it and the mobs wont be able to move what so ever allowing you to keep your line up. It sucks but I’ll let you know the scenarios where it is an issue.

mission 28 byakuya : you will want to use that [ ] / \ combo as mentioned above. Just wither down the bosses and try to avoid big damage things such as Soi-Fons sting and Barragan's O. on the final part with final form ichigo and butterfly aizen, try killing aizen last it saves a lot of time due to his death cutscene.

mission 19 byakuya : you will want to run to all 3 of the red officers in the level. (one on the far left as soon as you come in, one in the middle, then last one top right.) use 4 / \ specials on them to kill from afar. then for the boss gin and aizen kill gin first since he is bit of a slippery snake. Use the [ ] / \ combo on them.

mission 15 byakuya : the Menos Grandes can be killed quite easily, the crystal before first checkpoint has an ignition orb grab it. stand a bit back from the walls you must break. not to far back but just don't be rubbing your face on it. just pop ignition and do the good old [ ] / \

mission 8 byakuya : once you reach the mob fight with three turtles pull a hard right to line up two of the turtles then use your god old [ ] /\ combo. for yammy, just spam / \ /\ /\ [ ]. Don't lock on, it’s slower than just hitting his feet.

mission 3 grimjow : just run to mob fight. in the mob fight line up most of the enemies as you can then use you O (gran ray cero) on them. once you reach the boss just use 2 ignition Desgarron on him. if you don't have ignition after mob fight the crystal to the right of the wall you have to break has one for you.

mission 9 grimjow : just run to the rudobon mob fight. do a short hop Desgarron it should kill. AS SOON AS YOU ENTER THE BOSS FIGHT HIT THE O BUTTON. this cero is very important in one breaking the crystal with the ignition orb and hurting Barragan with enough damage to one shot with ult.

mission 12 grimjow : so as soon as you enter go right then right again there will be a crystal with an ignition orb. use it then use the tech above to shoot the officers threw the walls. there is one in each corner pocket here's the route I use. the bottom right then go back to the bottom left square. while going to him line it up as you dash. then go up to the top left line it up threw the bottom wall. then last top right. for the boss just hit the smaller one with a Desgarron then with your ult. ( if you need a visual take a look at my run here for mission 12 )

mission 4 byakuya : just get the ignition crystal on the left before leaving the first area. the same old same old [ ] /\

mission 1 byakuya : ok so a bit tricky but you'll want to use your / \ 3 times to the menos that spawns first then as soon as it dies turn around and shoot your / \ straight down the middle of the hallway. if lined up right ill be just a bit faster then grimjow. ofc for the boss [ ] /\

mission 5 byakuya : while walking to the other side of the area, shoot and kill the 2 flying hollows. If done right, you'll be on the other side and there's an ignition crystal to use to speed up killing kokuto with the basic [ ] /\

mission 14 Harribel : ok as you dash to the stairs you'll want to use a charge square to get the first 5th of the ignition bar. then go right. charge square ever single enemy you can till your bars full. book it to the end where there's 4 rooms. go to the top right room that one only has 8 giants. use ignition. then go to the back of that room you should be able to use your cero / \ two times and kill them all. if you don't its ok just cero them all. then go to rudobon witch will be in the middle now. just use your jumping O move. If some how out of sp use her jumping [ ] its deceptively strong.

mission 20 Barragan : go to the left turtle. Use your ground O (death by age) then to the middle turtle. there will be a crystal with an ignition in the same place as mission 5. Use it then spam charged [ ] and jumping / \ to kill the turtles. then 2 giants will spawn. just run up to them and use 2 charged [ ] they should die from the permanent death by age on you. Now just hurt skullclad ichigo and kokuto a tiny bit then ult.

mission 16 Barragan : Ground O the turtles. For the fishbones try to round them up and again use ground O. right before exiting the area there is an Ignition orb in right crystal. Hurt the bosses just a tiny bit then ult.

mission 18 yoruichi : just spam jumping o to get around. for the bosses just hurt them about a third of there health then ult.

mission 13 Harribel : just dash dash dash, once at the boss spam cortando ( your / \ )

mission 7 final form ichigo : just run to the middle of the map. then spam /\ /\ /\ [ ]. this will throw your 3 air slashes then cancel the recovery giving you a bit of sp back. just make sure your locked on and spamming use your ignition once your about low or about 50 beat count. for the boss you can just ult him if you want. if you feel you can kill him faster then 12 seconds then do that.

mission 2 final form ichigo : run to the mob fight. top left crystal in the mob arena has an ignition orb. use it then just spam your /\ /\ /\ [ ] till there dead. for the 4 officers at the end kill the first one. then as you wait for the next 2 to spawn go to the top left area right beside where the left officer spawns. if you space your /\ out you can have your / \ hit all three at once giving you a good time.

mission 6 final form ichigo : for the mob fight basic /\ /\ /\ [ ] spam. then once you reach the area with 3 boxes go to the left one first. get you a ignition crystal if you still don't have it ready (top left area) and be easy two / \ for all 4 of the officers. then go the middle one to fight bankai ichigo. easy just spam your /\ /\ /\ [ ] then hit up the last square which would be rukia. again spam your combo.

mission 23 final form ichigo : ( DO NOT USE IGINITION TILL TOLD HERE ) there's no dashing here so just walk your way all the way to the mob fight with rudobon and the hollows. just spam your /\ combo till everything it dead you should have ignition (if not there is one in the crystals before the next zone i believe). ONCE YOU ENTER POP IGNITION then ult. they will be perfectly lined up as they are spawned. more reason as to why in the things to know section at the top

mission 26 final form ichigo : if you want to you can use megutsu in the boss as soon as you go in like before because they spawn in the good order. just keep in mind you'll need to pop ignition when your IN the boss fight and then ult. basically just save it spam L2 once you enter. then do some clean up on the remaining bosses. leave Sajin for last. now for the mob fight basically as before ///\ [ ]

mission 21 final form ichigo : just dash to the mob fight and again ///[ ] the mobs. in the boss fight there is a ignition crystal in the back of the fight. just dash complete straight to the back ignoring the bosses. then turn around and line up the mugetsu.

mission 24 final form ichigo : DO NOT USE TILL TOLD! The very first crystal you see is an ignition crystal grab it don't use it yet. go to the mob fight with the 2 giants and 2 menos. just spam them down. I'm pretty sure its 7 /\ for the giants and like 3-4 for the menos. now as soon as you enter the boss fight spam the L2 button for ignition. then keep spamming for mugetsu. the 3 bosses are in a perfect line up.

mission 27 final form : ok so you will want to get some hollows behind rudobon and use your ground O attack to hit him and the hollows, you should get your ignition from this. if not you'll have to either use charged [ ] or just go fight the bosses till you have it. if you do get it how ever save it go to the room. now activate but don't use your ult yet. dash forward a bit. if soi fon comes towards you use it if not sorry to say you'll have to line it up for the 4 bosses.

mission 17 final form : want to know something fun? its not this mission ill tell you that. so just dash forward get your ignition crystal and save it for when your low on sp, the small building to the left of this crystal has a sp orb as well. spam your /\ /\ /\ [ ] combo on the flying hollow fishes. that's it, there's nothing else just a min and a half of killing 200 of these things. I would stand on the building with the sp crystal and spam your combo from there. since it is nearest the most spawns and the pathing ones come near it. also allowing for another top off once out of sp again.

mission 11 final form ichigo : as soon as the mob fight is started the crystal right in front of you is a ignition crystal. grab it you can use it since stark and shunsui need to be lined up anyways. so keep going till you get there. after the turtle mob fight take the left and not the right. once in you have to line it up. I find going to the left of shunsui is a good way to do it.

mission 22 final form ichigo : go to the right side of this fork. once you enter the turtle mob fight kill the turtle in front of you. the crystal behind it is a ignition crystal grab it DO NOT USE IT. once done with turtles enter the next area. now use it and keep spamming L2 to use ult before they can move. if done right it'll hit all 3 100% of the time.

mission 10 final form ichigo : go left on the fork, kill the harm flers. then before going to the next area the crystal to the left is a ignition crystal. grab it DO NOT USE IT. keep going to the next mob fight and kill the giant. then go forward and enter the boss. again there all ready lined up for you so as soon as you enter spam L2 to activate ignition and keep spamming to use your ult.

mission 25 final form ichigo : ok go to the mob fight and kill the arrancar sondeo. watch out for the turtle he is a pain. once done with the room keep going. the hallway you enter after the mob fight has a crystal at the end of it. before you turn right grab it and use it before or once you enter the boss fight either or is fine. your going to have to do a manual line up. keep in mind how large it is. i found a good way is to dash forward a tiny bit then aim for the middle of the group do not lock on it'll mess up your line up. if you cant get it you'll have to dash around till there in your line.