I am not familiar with ATX PSUs, but the question is, I reckon the 5V would deliver 5Amps, but what about the others voltages. They are also fixed voltages, so how are you going to make them variable.
There is a good argument , that if you have the circuit diagram, you couls strip all the secondary windings and rewind just one to give you your 5A, The number of turns would give you the voltage, and then you would have to modify the mark/space ratio of the main inverter circuit to reduce the voltage.
It will not be quick or easy or cheap, but once you have done one , then subsequent units would be very cheap and quick to reproduce.
Starting from scratch a mains transformer, regulator chip and a some power transistors on a heatsink would get you up and running with a couple of days, not efficient electrically but very efficient in time !
Frank