Tough to just go with one, the WWE has produced so many great themes, mostly in the original PG Era and Attitude Era. I'll just pick out some off the top of my head right now.
Stone Cold & The Rock (any versions) - That would just get you to pop and blow the roof off as soon as their intros hit. And some other poster put it best for Austin, whenever you hear that glass shatter, you knew somebody was about to get their ass handed to them.
Jake The Snake - His theme was just epic, sounds like something you'd hear in a oldschool classic movie, like maybe Escape From New York or something.
http://www.youtube.com/watch?v=edmNpPrwjlQ
The Corporate Ministry - Both their themes seperately were good but remixed together, it was just awesome. Would give me goosebumps everytime I listen to it.
http://www.youtube.com/watch?v=1ZZLwl6zZSI
The Union - For such a short lived and underrated stable, they had one badass entrance song.
http://www.youtube.com/watch?v=4lfEmPvFiXY&feature=related
But there are tons more that I could pick out, if I went back and thought about it long & hard, would take me like a week to list all of em.
As for, Raw, PPV & match promo themes, I'm more of a fan for the themes that WWE produced for them in the PG & Attitude Era's than the ones produced now. Some themes off the top of my head
http://www.youtube.com/watch?v=JqQb7cfBaA8: All Together Now (Raw Is War theme)
http://www.youtube.com/watch?v=LBFSojGkLtg: Thorn In Your Eye (Raw Is War theme)
http://www.youtube.com/watch?v=saF5DFelWF8: Nine Lives (No Mercy 99 UK theme)
http://www.youtube.com/watch?v=HWrPgjOkXDY: On The Tracks (No Way Out 2000 theme, also used in match video promos)
http://www.youtube.com/watch?v=Sw19xA5TrWE: Rage (Wrestlemania 15 theme)
http://www.youtube.com/watch?v=xporEvGxWn4 (used in a lot of Stone Cold video promos)
http://www.youtube.com/watch?v=pLF6Gfjb03g: Death Race (Royal Rumble 1998 theme, god this gets my so hyped up everytime I listen to it)
http://www.youtube.com/watch?v=2vr9fdFz4qY: Classic Wrestlemania theme
http://www.youtube.com/watch?v=egu203Fld94: Classic Wrestlemania theme #2
Just like with the entrances, I can name tons more classic Raw/PPV/match promo themes from the PG/Attitude Era.