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What are the most popular or best rule sets out there for 6/10mm during the Napoleonic and dark ages?

Peter pigs' bloody barons looks nice, shame they don't have Napoleonic rules...

Popularity is regional, so you're going to have to find local historical players around you to answer that question.

I like Dux Bellorum by Daniel Mersey. It's part of the Osprey Wargames Series so it's widely available through book distributors.

http://boardgamegeek.com/boardgame/88079/dux-bellorum

It's a simpler game that plays fast. It uses elements with the number of figures not really mattering, so just use as many 6mm miniatures as you want on a base and adjust your base sizes based on your table size.

http://www.amazon.com/Dux-Bellorum-Arthurian-Wargame-Wargames/dp/184908680X/ref=sr_1_1?s=books&ie=UTF8&qid=1411254243&sr=1-1&keywords=dux+bellorum

For Napoleonics, it's a matter of what scope you want to cover. Tactical where you are manually forming battallions into different formations? Or perhaps a grand tactical level where each maneuver element is an entire brigade and you are refighting an entire battle rather than a subsection of it?

I like the Marechal de l'Empire/General de Brigade twin ruleset from Polemos. Designed for big 6mm battles. I'm not sure how popular it really is. Worth a look, though.