After rereading this posting.... my thoughts about testing.
Minimum needed to test for post/boot up.
1. Motherboard.
2. CPU with heatsink.
3. 1 Memory module.
4. Power supply.
5. Monitor.
6. Keyboard.
Install CPU and heatsink (with TIM) and plug in fan to CPU Fan connector.
Install one memory module.
Plug in 24 pin power connector AND 4 pin CPU power connector.
Connect monitor and keyboard.
Connect a switch to the motherboard power header pins OR CAREFULLY short the two pins together with a small screwdriver or equivalent.
If this gets you a display on your monitor, then you can add other items to your system.
As for the purpose of the added 4 pin CPU connector, it adds 2 extra 12 volt power lines for the CPU to draw power from. Some boards may boot without this connected.
As for the motherboard LED, that indicates that the power supply is powering the MB with a 5 volt standby power. This standby power allows among other things, for the keyboard to turn the computer on or to power on or Wake the computer via LAN.
Ok, I'm done for now.....