Sure, I'll give it a shot.
But that's exactly what I'm doing. Kaine and the hostage have been disguised as attacker and battered victim. (And incidentally the bank is even a crime scene, albeit a crime in progress rather than after the fact.)
I'd think Psychology would be less deception specifically and more knowledge of behavior in general. So while I can absolutely see Mysterio using it to help his illusions, I would think it would be more 'I know if I put up a flashy display over here, people will go look at it, and not pay attention to other stuff' or 'I know if I'm fighting Spider-man and I shove someone off a building before I flee, he will go to save that person 100% of the time rather than chase me.' But if this version of Mysterio was an actor he could then also use it to determine 'if I put a nudity scene in my new play, it will draw more of the 20-50 crowd but there won't be any families showing up.'
I guess what I'm saying is I think there's some overlap between the two.