As much as I like to be a smartass or provoke my Master from time to time, I'd never conciously break any of his rules hoping to be punished. I've found out early on in our relationship that the punishments he deals out are not ones that make me hot...quite the contrary. I feel miserable when he's disappointed and know I won't enjoy the consequences.
The punishments I've had to face so far were mostly time outs, sometimes combined with some pain (that I don't enjoy at all when it's in serious punishment setting). And believe me, those get me back in line extremely quickly. His disapproval and disappointment alone are bad enough, but having to spend some time without distraction thinking about where I've gone wrong and how to avoid making this mistake in the future make it a tough punishment to go through.
Other punishments I've experienced so far were writing lines for a TM at the academy (and in that case it worked quite well to achieve the right mind set)...a time out from any playtime for a few days (contrary to just orgasm denial which can be pretty hot, this was indeed punishment and I didn't want to risk that particular mishap again, lol)...wearing a plug for an extended time (not really that effective since I usually like it)...spanking of tits or inner thighs (yeah, effective for the moment...but I DO love the marks afterwards, so I guess that's a downside for the desired effect *grins*).
What ruins any punishment for me is when it's combined with anything pleasurable during the scene...afterwards - fine, but I remember a dom I played with online for a bit and he liked to tease during the punishment and hell, did I want to get more of this later, lol.
I really think the key is for the dom to know his/her sub very well, know what activities will be good punishments and which ones might hold secret pleasures.
*shudders* I really don't like punishments. The only good thing about them is that once they're done, it's over and the subject closed.