Most Helpful Girl
It's Spider-Man. With a hyphen. There is no such thing as Spider Man. (Well not in the Marvel world at least.)
Spidey never kills if he can help it so one-on-one Sidious would probably have an edge on him if he weren't holding back and was willing to go that far. I think he'd have a tougher time against Captain America though.
Most Helpful Guy
Darth Sidious was a punk bitch. Vader is probably the most badass villain of all time. But Sidious would probably win because he'd just blow up whatever planet those characters were on.