If there is an option in the BIOS under the power settings, then altering the switch isn't necessary.
There should be something similar to this under the power options of the board. It might read the following.
PWR-ON after PWR-FAIL. If this is enabled, the system will start automatically when the switch is turned on. At least that's how it is on my PC. I'm using DOS though, so that's really not a problem with the PC just turning it off and on. I have it wired to the power block, so when the marquee, and monitor get juice, so does the pc.
Try looking in your BIOS before making any mods to the switch or PS.