The best way to see if you have used the proper amount of TIM is to use a temperature monitoring program like coretemp. If your temps are below 60C under load, you should be okay. Keep in mind that too much is also a bad thing. You can always reseat your heatsink if it is that much of a worry. Although high temps can cause thermal throttling and some hardware freezes, I would be more inclined to suspect the PSU.
The PSU is truely the lifeblood of your computer and voltage variations can easily cause BSOD's. It would also easily explain your every-other-time startup issues. If you have a quality PSU, I would see if you are still under warranty. If you do not, now would probably be a good time to invest in one. I cannot say for sure that is your problem but that is where I would start.
When looking to purchase a PSU, do not go strictly by brand - even quality brands like Seasonic, Superflower, Corsair, FSP come up with duds now and again. Check out the exact model's reviews from JonnyGuru, HardOCP and HardwareSecrets - those reviewers actually stress the units, tear them apart to see how they are made and the quality of the parts and build, fascinating reading. Or, look up that model PSU review by them and skip to the last page without reading the filler, either way, you shouldn't go wrong.
http://www.jonnyguru.com/
http://www.hardocp.com/reviews/psu_power_supplies/
http://www.hardwaresecrets.com/page/power
Check your temps with Coretemp and happy reading