For a square hole, the best bet would be drilling the largest diameter hole you can where the switch would go, and then filing off the edges till square, or, by using a small hacksaw (usually a few pounds/dollars/etc).
I've done exactly what you want to do to one of my old power supplies, but luckily it already had a mains switch.
The power supply should have a cables hole at the front that a nice circular hole you could slot a round switch in?
On my converted psu, you can see the green switch i put in the cable hole, it fit perfectly and switches it of nicely
Hope i helped.
EDIT - sorry for the very large photo, not sure how to resize