<< What is the purpose of a relay to hook two PSUs together on the same switch? >>
To power up both power supplies at the same time while still keeping each circuit separate.
<< can i not just hook the hot and a ground from a molex of 1( the one plugged into the board) into the green and a ground of 2? >>
No, that's not the same as grounding the green wire. Your method would try to deliver 12V to the green wire on the second PS.
Think of it this way. You take the green wire and touch it to a ground on the same PS. The PS turns on.
Now, imaging taking the green wire and a ground wire and placing a 12V battery between them. Doesn't sound right, does it?
Not only would it not work, most likely you will fry something.
<< do i need the 12v relay in between? >>
Yes. That is the only way you can ground the green wire using another PS.