This is funny, just the other day I was worrying about this same issue only with an embedded computer, pc/104.
First, go here: http://www.formfactors.org/formfactors/atx_ps.htm
and download the pdf. On page 18, it will talk about a signal PS_ON#. This is an active low signal(meaning you have to ground it to turn the PS on). Then on page 27 it will show the schematic of the ATX molex connector. All you need to do is short/connect the PS_ON# pin to COM(ground).
I did this on Friday, and it works perfectly. Good luck
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