I was about to say Skywalker solos with incredible ease, but then I realized we're going with movie feats only.
This one is tough to call. Generally speaking, all four of the characters in this fight are much weaker with their movie versions.
The HP movieverse uses very little creativity in combat spellcasting. Most of what they end up doing is basically like the Stupefy curse. The curses like what they use are generally pretty straightforward concussive (can be blocked by a vibranium shield) and projectile-style (can be dodged). I don't see Harry being very highly effective unless he gets on his Firebolt and shoots from the air.
Luke loses pretty much all of his best feats if he's restricted to the movie version, but he is still a force to be reckoned with. For the sake of a good fight, I'll assume vibranium will block a lightsaber. Having the force gives him the speed and pre-cog necessary to keep up with Cap and Spidey. The real issue is his morals. It's against Jedi code to kill or injure an unarmed opponent. He may be fine with hurting Cap, since the shield counts as a weapons, but would he hurt Spider-Man? Spidey's webs in the Raimi movies were organic. He did not have web shooters or anything else that could be construed as a weapon. I think Luke might hold himself back if engaging Spider-Man.
Spider-Man is far inferior in the movies. He is slower, weaker, has an inferior spider-sense, and limitations have been put on his webbing. I can see him being able to dodge Harry's spells in the beginning, but he would have a hard time of it once Harry sees how quick he is and adjusts accordingly. Spider-Man will have to get up close to be effective against either enemy, and the wide-open spaces of the football field don't give him the best chances of getting up close.
Cap, IMO, is the powerhouse of the fight. He can block offensive spells indefinitely (unless Harry uses something more creative, like "Accio shield". But he never really did that much in the movies), block the lightsaber, potentially knock Harry off his broom with a good shield ricochet, and he is strong enough to KO either enemy if he manages to land one solid hit.
In 2v2 battles, the usual style is for fighters to pair off from the start. Because of that, there are two potential scenarios I see.
Scenario 1: Harry vs Spidey, and Luke vs Cap.
Due to Spider-Man's lack of truly impressive speed/agility or a really good spider-sense in the movies, I wouldn't actually bet on him being able to dodge Harry's spells indefinitely. His only chance is to snag Harry's broom on a web in hopes of throwing him off, but even that plan could have some big hitches. I can see Harry beating Petey. Luke vs Cap is much closer. However, one has to remember that, even in the movies, Luke was capable of beating Darth Vader in 1-on-1. He has a small edge in both training and experience to Cap. Cap is stronger and faster, but I can still see Luke taking an extremely small majority.
Scenario 2: Harry vs Cap, and Luke vs Spidey
Cap would beat Harry. He can block concussive spells all day, and has the speed and presence of mind to knock Harry's broom out of the air. Luke, on the other hand, would probably lose to Spider-Man. He would hold himself back significantly, and would probably be disarmed at some point by webbing.
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