This is all all-around Psylocke romp. Not only will she smash on Captain America in both incarnations, but she will look good doing it.
Classic Psylocke can control Cap's brain and then the fight is over.
Cureent Psylocke can "smash mountains" with her TKE. She uses it to modify her strength and has excellent hand to hand fighting ability. Cap America has no way to get through her TKE shield so there is no way he could even lay a finger on her. Cap's lucky she likes to fight; otherwise Psylocke would just crumple him into a tiny ball with her TKE and leave.