This scene is stupid as fuck, of course. Spider-Man is more than ten times as strong as Captain America. I'm sure he's faster too, and on top of that he literally predicts the future with his overpowered as fuck spider sense. Who needs martial arts when you predict all your opponent's moves before they even make them, and your body reacts faster than theirs can even move? Captain America trying to hit spidey should be no more effective than any other single opponent trying to hit him.
Of course, Spider-Man has always had the opposite problem from the advantage that that Captain America has. Where cap always somehow manages to stand up to opponents who should tear him to shreds like he's not even there, spidey has a long history of getting his ass handed to him by opponents who shouldn't stand a chance against him at all. Yeah, somehow he can dodge multiple assault riles at close range being shot straight into him, but if doctor octopus throws one of his stupid mechanical arms at him (or captain america tries to land a super slow blow that spidey can see coming from miles away) spidey is like a deer in headlights. I guess they're a perfect match for each other, in that sense.
Anyway, that's all besides the point I was trying to make about Captain America's real super power being his plot armor and plot weapon, which keeps letting him fight opponents that shouldn't even notice that he's there.