First of all. The Russo Bro's have way buffed Cap in all their movies. The stuff they have him tanking and doing makes no sense. Not complaining about him being worthy (that makes sense). But that said:
Thor... Thor wins even with Cap's plot armor. Cap might have better H2H skills like people are saying, but Thor has been wielding magical weaponry for thousands of years so he has way more experience with the likes of Mjolnir/Stormbreaker. Thor's also WAY stronger and WAY more durable (fist fighting the Hulk multiple times/tanking a direct blast from the heart of a dying star), and he has native lightning powers outside of what the weapons grant. He could one shot KO Cap with a punch or one shot kill him with either weapon. Thor could take multiple shots from either weapon (except maybe the blade end of Stormbreaker). Also, logically Thor has a more powerful claim to Mjolnir and could likely call it away from Cap if they were both competing for it.
Honestly the only thing that keeps Cap from being one-shotted immediately is that he has his shield which can absorb the impact from Mjolnir or Stormbreaker's hammer end. But Stormbreaker's blade end can likely cut Cap's shield like Thano's blade did.
But for the sake of giving Cap a chance lets say Thor can't call it away from him while he's holding it (and the reverse). So Cap has his shield in one hand and Mjolnir in the other. He's not going to catch Stormbreaker unless he drops or throws one of them. If he swaps his shield for a chance to catch Stormbreaker then he's just lost the one thing keeping him from getting one-shotted. If he drops or throws Mjolnir he's basically giving it to Thor. Most likely he'd retain both to be able to defend and attack effectively. Thor probably just moves forward hacking with Stormbreaker for fear of losing it. He'll tank Cap's Mjolnir attacks and Stormbreaker's blade end> Cap's shield with enough strikes. Cap can't really hurt Thor. He can't physically throw the hammer nearly as hard as Thor can and Thor won't be damaged by Mjolnir's lightning as it's native to him. One could argue since Thor is worthy he likely wouldn't even take physical damage from Mjolnir if he called it each time Cap threw it/swung it. But Thor could launch Cap with a shockwave impact from Stormbreaker and then swat him off planet while he's airborn. Or just get his hands on him and physically crush him.
In the end, unless Cap gets his hands on Stormbreaker he really doesn't have the offense to hurt Thor. While Thor has tons of options for hurting Cap, he just has to get through/around the shield which is bound to happen at some point.
If Thor can call Mjolnir away from Cap then it's game, set, match. He could just retain both Mjolnir and Strombreaker and use them as melee weapons. If he doesn't throw them, Cap can't catch them and use them as Cap's claim to Mjolnir won't outweigh Thor's and Stormbreaker is different so it won't just go to Cap without him picking it up or catching it first. If Thor has both hammers then Cap has no lightning powers, so Thor could just spam Stormbreaker or native lightning and fry him. Or Thor could just call Mjolnir and throw both hammers across the galaxy and then manhandle Cap before he can call Mjolnir back.
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