For this achievement, you actually have to get Super Hero on every mission on the hero's side but also Super Villain on every mission on the villain's side.
Just play every level with the following extras turned on:
Score x2 Multiplier N4NR3E
Score x4 Multiplier CX9MAT
Score x6 Multiplier MLVNF2
Score x8 Multiplier WCCDB9
Score x10 Multiplier 18HW07
You should get this achievement and the "Richest Man in Gotham" achievement on the way as well.