Pete for sure now
At this point in Spider-Man's development, he's still unable to stomp Cap. Iron Spider suit tilts the fight in Peter's favor, but I wouldn't be surprised if he messes up and losses. Skill matters a lot when both fighters can consistently harm each other. Vibranium is not joke and I'd bet it could hurt Peter through the suit, though not much else Cap has really can. It all depends on how Peter plays his cards.
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