I know it's possible to manip some characters. I don't know about their positioning, but their behavior I can manip.

For those characters who tend to defend a lot (parry/counter, e.g. Squid, Kyabo, Mina, Pixie, Boris, Chester, Nino, red bots), just throw a slow throw first, then a fast throw. The AI will react to the first throw and try to defend and whiff, therefore your 2 throws will freely hit. AI uses defense based on button input instead of throw distance and velocity.