Walter,
I opened up an 8600 and tested the leads. The main molex connector does not get power until the power switch circuit is triggered on the motherboard. It is a momentary switch so the circuit is only closed temporarily, long enough to signal the relay in the power supply. If the large Molex connector is disconnected from the motherboard, the relay in the power supply will give an audible click. Every time. Pushing the micro switch on the motherboard is preferable to pushing the spongy switch on the face of the case.
The power supply will not activate if the large molex is not connected to the motherboard. I did not trace wires to see exactly which lead(s) trigger the relay. On and ATX PS for a PC, I would tell you to jump the purple and black (I think - don't quote me on that!).
As for color coding: The trickle charge ( trickle only because that is the limited draw placed upon it, not because it is any less 5 volts than any other 5 volt connector) comes from the yellow lead in the Small Molex connector. Or, the trickle charge is not 5 volts and comes from the purple lead.
Using this link as a reference,
http://www.macgurus.com/products/motherboards/mbppc8600.php
here are the relevant specs:
Small molex
There is a green wire, a purple/lavender wire, then a yellow wire coming from the upper right hand corner of the small molex connector labeled in the diagram as the 3.3 v. Power Supply. The green reads zero. The purple reads .548 volts. Note, that is less than one volt, not a misplaced decimal point. The yellow reads 4.99 volts. That is your 5 v lead. This is irrespective of the existence of any PRAM battery and does not depend on the large molex connector being plugged into the motherboard. As long as the AC power cord is plugged into the power supply, you should get 5 v at the yellow lead to the small molex.
IF the large molex is connected to the motherboard, and the power supply works, the machine will start up, even if the PRAM battery is physically removed from the building you are in.
(PRAM batteries are important and computers work better when they are fresh but I have never needed a PRAM battery even near any macintosh computer I have ever tried to start up. Ever. The advice to have a fresh battery is good but does not apply to your case. A warm boot gets me around a dead or missing battery every time.
So, You either have wall power or you do not. Tracing it from the wall outlet, into the power supply out of the transformer to the yellow lead going to the small molex connector will tell you if the relay will ever turn on and trigger voltage to the rest of the motherboard. Anything else assumes that the power will come from positive vibes floating through the atmosphere. : )
Bonus link:
http://www.eserviceinfo.com/downloads/13992/Apple_Power%20Macintosh%208600/9600/ WorkStation9650.html
Good luck as always.
Jim