Meh, Cap fighting and taking it to some super soldiers without his own SSS is impressive, but not a fair analogy- those soldiers are built and made to fight exactly like Cap does everyday, and it's no surprise that he would know exactly how to avoid being struck by one.
While he's familiar with Spider-Man's fighting style, the way that Parker moves and strikes isn't nearly as uniform as those soldiers or even Namor (who Steve really has no business taking it to in hand to hand combat, but whatever). Further, unlike nameless cannon fodder, Spider-Man is being treated in this discussion almost as if he doesn't have decades of crime fighting under his scarlet belt. It just comes off as a little crude to suggest that even with doubled speed, durability and what should be an insurmountable gap in strength and agility, that Parker lacks the sheer competence to hold up in a fight against Cap.
I agree, Steve is ridiculously more skilled, but I think Pete passes a threshold of competence as a fighter after which one would need to either become superhuman on a level that competes, or forfeit the battle. He knows how to roll with a punch and he knows how to deliver one, and he remains more than fast, agile, durable and competent enough to ensure that regardless of Steve's skill, he'll always be capable of reacting in some respect before struck.
Which, incidentally, is why nerve strikes sound bogus to me as an argument to be made here.
I realize martial artists like Karate Kid defy this logic, but I think those cases should be left as outliers and not used as an example for comic book fights across the board. I'll probably hear otherwise though.