I just built a Quad core Q6600 PC with an Asus P5K-E wifi motherboard and it has problems powering on. It works fine when it is on though. Basically you need to either hold the power button anywhere from a second to a minute or press it several times (sometimes even 100, no joke) before it turns on. Once its on, its fine. What could be the problem?
Probably a dodgy contact in the power switch or with the connection to the board. Check your front panel connectors are secure and try and inspect the switch from inside the case if possible. Which case are you using?
I am using some XION case that I used to use with my Celeron before I got the quad. It worked fine with the Celeron.
I also don't think it is a power button issue because it only happens after turning it on after a long break such as overnight. If I turn it off and turn it back on 10 minutes later, it will work. Also the power button works when I turn it off using it.
Motherboard Issue? Not getting the current quick enough to the PSU? Overclock problem? Incompatible RAM?