I'm not sure I'd place Cap above, say, Black Panther or DD. Cap's greatest asset is his ability to learn skills at an incredibly fast rate. Just looking at his h2h skills from the Avengers to those shown in Winter Soldier (seemingly no more than a few months later), indicates he learns quickly. But honestly, I'd attribute that to the serum (it's suggested the serum enhanced his mental abilities to a degree). Meanwhile Black Panther is arguably at his level. If we were to compare their respective fights with Bucky/Winter Soldier, T'Challa did just as well as Cap. (I recognize their objectives were different: Cap just wanted to stop him or defend himself, T'Challa wanted to kill him.)
As far as Bucky himself, I think his skill level heavily depends on whether he's of the "James Barnes" mindset, or the "Hydra assassin" mindset: when he's on the run, or just Bucky, his skill more resembles 1945 Cap's. He throws punches, kicks, and blocks, but no technique beyond that, and barely escapes getting torn apart by either Iron Man, or Black Panther. Then, when he's in the "mission only" state of mind, he manages to show very calculated, targeting skills, chocking Black Widow, harming Stark, Cap, Black Panther, Falcon, Widow, Sharon Carter, and several German Embassy soldiers in rapid succession, contending with/grappling Cap (once stabbing him in the subclavian artery).
As the Winter Soldier, he's in tier 2, somewhere beneath Cap& Black panther, but above Black Widow.
As Bucky, he's a bit further down the list.
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