Depends on the surface areas and geometries of your VRM parts. If there's a big gap then a thermal pad or goopy thermal adhesive might be better than a thermal paste. If there's a very smooth and tight gap or an irregular interlocking mating surface then a thin and runny TIM (like Gelid) will flow into the gaps and provide better overall coverage. Good old AS5 is pretty good stuff, too.
You might see improved temps right away, but don't expect best thermal performance for a week or so - any liquid-paste-grease TIM you use will need some curing or dry-out time before it really starts working, this can range from hours to days.
I clean my part surfaces thoroughly, of course (as in, I obsess about them being absolutely clean, mechanically and chemically, no oils, no debris, no residue) and I scrape the TIM on with a (clean) razor blade - but so-called "pea" and "X" and "rice" and "dot" methods are all acceptable on larger parts like CPUs and GPUs. The key is to use the *minimum* amount of TIM you can to achieve full thermal contact, it transfers heat better than air/bubbles/voids but not as well as the metal heatsinks themselves - most people think more is better so they apply too much and see only marginal improvements in temps.
Noctua's TIM is generally not considered all that great. It's probably just some branded cheap stuff they make so that people have everything they need in the box when installing their new Noctua coolers.
You'll find that TIMs are a controversial topic, many people will champion their chosen TIM product zealously, many will promote or condemn TIM products based on reputation alone. All I can say is that I've used plenty of TIMs in plenty of devices, and the stuff sold for PCs is really no different than the stuff sold for other electrical devices.
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