In hand to hand combat and or weapons (No firearms or eye beams). By skilled I mean using their abilities within the concept of a martial arts. Although Spiderman is an incredible fighter I would say people like him do not make the cut makes the cut because of a lack of formal training. Someone like Blade however, although not the best within martial arts, due to his abilities would allow him to make the cut.
In the Marvel universe I would say Wolverine.
In DC universe I would have to go with Lady Shiva (Batman being a close second)