Well, things have moved on a little since my post of despair yesterday lunchtime.
I was on the phone to my pal and we were discussing all options, theories etc. I trawled the web and found many differing opinions for many different types of engine. Leaks, fine mesh on pickups, pump, oil viscosity and more. I was going with the thick oil and fine mesh on the pickup, but that would have ruled out the same issue when hot. I thought about buying a new std pump, instead of the high capacity Turbo one I had selected. I reckoned I could do the swap in an hour.
If someone had said, strip the engine again and fit this, It'll cost you a few hundred quid and it's guaranteed to work, I would have done it!
The unit was in the car and with no real alternative direction to head, I connected everything up and decided to see what I got when running. Remember originally, the engine ran fine and gave acceptable pressure readings whilst running.
Apart from all the gaskets & new shells, the only change was the new ball bearing relief valve. I had tried this remember pre full strip down but only on the starter.
Engine fired immediately, 4 - 5 seconds and I was off the gauge at 100psi.
Switched off, removed the relief valve spring & ground some off. Back in and now at 90psi. Same process again with a little more from the spring removed.
Now here's where everything changes. Press start button, instant out on the light and 80psi at tick over.
On / off a few times, leaving it to drain down and the light is going off straight away.
Packed up went to the pub, tried when came back a couple of hours later, spot on.
This morning, stood overnight, nice and cold. Less than 2 seconds. Took the plug from the coil pack, and I can get 75psi on the starter 
So am I jumping for joy? Well not really, (I am happy & relieved though), but I don't know what I have done to cure it.
Did the 100psi run dislodge or move something that was originally sticking? Could my issue have been the original relief valve bullet, which had some minor marks but was ruled out because the pressure was okay on run?
Did I solve the problem when I fitted the ball, but it needed the engine to run to prime properly?
I'm really glad it seems "fixed", but don't you just hate it when you don't know why?
Best get the rest of the bolts tightened now and the drive shafts back in. I need some miles before a RR session.
Thanks to everyone who offered suggestions. If my joy is short lived, I may be back.
Regards
Steve