1. Captain America
2. Batman
3. Daredevil
4. Spiderman
5. Wolverine
Cap and Batsy may be too close to call. Batman has the equipment advantage. But Cap's use of just his own body and its resources is better. Then again, Batman will use tactics that Cap won't. Ultimately, the fight depends on which Batman shows up that day, but the pure skill edge probably goes to Captain America.
Daredevil edges out Spidey because a lot of Spidey's prowess comes from his powers, while DD's comes mainly from himself. Spidey would wipe the floor with Daredevil, but it would be because his powers are greater, not his fighting skill.
Wolverine, despite the fact that he might take all of them, has less skill. Despite his military training, and all the references to Samurai and Ninjitsu, etc., Wolvie is a brawler at heart. He wades into fights, delivers a pounding, and usually takes an even worse pounding in return. But that doesn't bother him because of his healing factor and the fact that he thinks he deserves the pain. I may be doing him a disservice. If his past can be believed, he probably is a LOT more skilled than this, but he doesn't use it.
btw- Silverthrone, I have to disagree with you on the fury part. If anything, Wolvie has substantially lesser skills while in a berserker rage. He's just more ready to receive damage and dish it out without compunction, not more skilled. There's a difference. Wolvie's a Barbarian, the rest are fighters, except for Batsy, who's a Rogue/Fighter (eschewing prestige classes and 4CTF for simplicity of analogy

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