1. Double check to make sure you have all of the connectors from the front panel connected to the right pins on the motherboard header. In most cases, the individual connectors are labelled, and your manual should have a diagram of the header. Also, make sure you have all other connectors, including extra 12 volt connectors, etc, from the PSU connected to the motherboard and/or vid card (if required).
The power switch works by momentarily shorting across the power switch pins. If everything is connected correctly, and it still doesn't start, unplug the power switch wire pair from the connector on the motherboard, and use something like the tip of a screwdriver to short across the pins.
If it starts, either the front panel switch is bad, or the wrong lead from the front panel is connected to the header.
Note - All (or most) front panel wires are color coded with one colored wire and one common colored (usually white or black) wire. The common colored wire is the negative ( - ) lead. This only matters for LED's, etc., but it's a good idea to keep them all facing the same way if your motherboard connection diagram allows.
2. With the main power switch off, unplug and re-seat your RAM, vid card and any other peripheral plug in card. Then, power up, and try again.
3. With the main power switch off, unplug all but one stick of RAM, and try again. If it doesn't start, try another stick of RAM, and try them in different RAM slots. If you have other known good RAM (from another machine, etc.) that's compatible with your motherboard, you can try them, as well.
4. Your motherboard may be shorted to the chassis. To test this, remove everything, and with the case oriented horizontally, isolate the motherboard on the edge the chassis, isolated with a sheet of plastic or cardboard. Carefully insert just the RAM and vid card, connect the monitor and power switch connector (or use the screwdriver technique, above) to see if it starts. You don't need to connect a drive. You just want to see if the PSU starts and the CPU fan spins up.
If it starts, you've found your problem. Carefully re-install the motherboard, making sure all mounting holes are well aligned, install the RAM, vid card, and test to make sure it still works with the motherboard screwed down.
If it still doesn't start after all of that, if you have access to another PSU, try it. If the other PSU is in another case, you don't have to remove it if you can move the two cases close enough that the wires from the other PSU will reach your motherboard.
If it starts, you'll need a different PSU, but you'll have your answer. If not, the above steps should keep you busy long enough to give others a chance to reply with further suggestions.
Be very careful that nothing is shorting or touching other hot or grounded wires or metal while you're testing things in this loose, unmounted condition.
Hope that helps, and happy New Year.
