Oh, I see what you're asking now. You want to know what the main buttons are for N64 so you can line them up with the main buttons of your PSX Pad.
Here it is:
PSX -> N64
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X -> A
Circle -> B
Start -> Start
D-Pad -> D-Pad
Left JoyPad -> JoyPad
Right JoyPad -> C-Buttons
L1 -> L
R1 -> R
L2 (Because Z is commonly used to rotate the camera left) -> Z
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This setup is similar to the Gamecube controller and is probably the set up you're after. Enjoy

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