Wolverine
Wolverine would be a comparable teacher to Cap. They both have a ton of experience, so this is probably the closest matchup. Cap has a slight edge in tactics/strategy, Wolverine has the edge in ruthlessness.
Scenario 1: Cap's team wins a close one. Wolverine's team just isn't equipped for non-lethal measures.
Scenario 2: Toss up or slight edge to Wolverine, for opposite reasons listed above.
Thor
IMO, Cap has the edge against Thor in just about every relevant category. Plus, his team respects him more and works harder for him.
Scenario 1: Cap
Scenario 2: Cap
Punisher
Can't match Cap. Simple as that.
Scenario 1: Cap
Scenario 2: Cap
Batman
Batman is no doubt an extraordinary teacher when it comes to a single pupil (see Robins). If you dumped 50 people in front of him he'd consider them a nuisance and ignore them. After two years he'd solo Caps team.
Scenario 1: Batman via cheating
Scenario 2: Batman via cheating
Wonder Woman
Arguably the most skilled person here (I'd argue it anyways). Raised by a culture that does this, and only this, for a living. She has enormous experience and resources to draw on. She may not be the strategist/tactician that Cap is, but she'll have the best fighters. By far.
Scenario 1: Team WW
Scenario 2: Team WW
Orion
...gets confused and overestimates human durability. Gets pissed of a lot by their incompetence. His team dies in their training.
Scenario 1: Cap via forfeit
Scenario 2: Cap via forfeit