Really dumb thermalpaste question
How much time is between application and first start up doesn't matter. Won't make any difference.
The paste will be trapped in the impurities and denivelations in the two metal surfaces and help transfer the heat between the two metals. The amount of evaporation going on on the edges of the heatsinks is extremely small, practically doesn't matter.
A rice or a pea size is a bit outdated, you can put a bit more. Too little is bad. A bit more than ideal won't make any meaningful difference, it's like maybe cpu being 0.1..0.3c hotter than ideal case. A LOT is a bit worse... but you'd really have to go overboard with paste to be A LOT.
You can apply a bit more, let's say about as much as you see people in toothpaste ads apply toothpaste on a toothbrush.
edit: don't spread the thermal paste yourself as in don't use a ruler/card/finger to paint the cpu surface with thermal paste ... put a big blob in the middle, or make an X on the surface of the cpu, basically two lines of paste crossing each other. When you put down the cooler and gently press it down, it will flatten the paste and push it towards the edges so you won't have any trapped air bubbles between cpu and heatsink.
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