Is this a new build or was it working and just stopped powering on? Since you replaced the ps, which can just about rule out the ps as the source of the problem.
I would try for a post outside of the case. To do this remove the mb from the case and put it on the box it came in [do not use the anti-static bag; some bags the outer surface conducts electricity] Connect just the video card and one ram chip [unless you have RDRAM and need two] connect the ps both the twenty pin connector and the four pin connector [if used] Now find the connection on the mb where the power switch connects to and jump across the contacts with a small screwdriver. If it posts now, you know that you have either a mounting problem or a bad switch on the case.
As a quick test for a bad switch, I connect the reset switch to the connectors for the power switch. Push the reset switch and if it powers on, you know you have a bad switch.
If it does not power up outside of the case, you will need to start swapping parts with known good units ie mb, processor.
One last thought; make sure you have the hsf plugged into the correct fan header. Some boards will shutdown if they do not detect a fan signal. If this is a new build, make sure the clear cmos jumper is not in the clear position.