Spidey, any day of the week and twice on Sunday.
I was never a fan of Punisher. One might argue that he serves justice as a vigilante and those he kills have it coming, but that, to me, is not the definition of heroism. Dude's a callous, murdering thug with a gun; what's heroic about that?
Answer: big, fat nothing. Besides, Spidey would take the guy apart in the blink of an eye, regardless of what machination a writer might come up with to make Punisher fans think he'd have a snowflake's chance in hell against a guy who's taken down some of the heaviest hitters in the entire Marvel comics universe.