ATX Specs from Desktop FF
Page 19 section 3.3.2. explains the PS_ON signal functionnality.
Notice that it is not necessariliy high, but may just be opened when the PSU is off. The table says Vhigh is 2V min. It also says that the PSU shall have an internal pull up, so you don't have to provide any voltage, just to release this signal from ground.
For the 5VSB, I believe you can use any ground wire. Section 3.3.3. does not say much.
Hope this help.