The fuel pump along with the relay have been replaced. I have put a test light on the fuel pump with the key OFF, and the pump is not energized. That still does not explain why i have 100psi and the car still wont start on the first try once you do multiple complete ignition cycles it will start.
Did you change the fuel filter? Change the fuel filter, and measure the fuel pressure with the engi8e running and engine off.
A restrictive fuel filter, or fuel line, will have a higher fuel pressure before the fuel filter (or, line restriction), and a lower fuel pressure, after the fuel filter or line restriction, WHILE THE ENGINE IS RUNNING. With the engine NOT RUNNING, the pressures will equalize on both sides.
Sounds like vapor lock that air plane engines get. The fuel lines get hot when the engin is shut down, the fuel vaporizes and pushes back to the tank. Cant get them started until they cool some. You might check for a missing heat sheild or a bent fuel line to close to the engine.