What are the best in your opinion?

Waterloo - http://www.imdb.com/title/tt0066549/

and you can't go wrong with the Hornblower- and Sharpe series.

Depends on what you mean exactly with that. The closest to the theme is Abel Gance's famous "Napoleon". In the general setting, you have Ridley Scott's "The Duellists". On the sea, the magnificent "Master and Commander". If you just care for the very loose general context, you can try the cinema adaptation of "Alatriste" - not very napoleonic (it's like 2 centuries before), but still quite epic, with sword and musket battles in Flanders. I'm a fan of the novels, so, I have to mention it...

Sharpe series is awesome.

I enjoyed Sharpe as well good deal of action and adventure and think the part was made for Sean Bean.

War and Peace (1967 version, not the PoS 1956 version with Fonda/Hepburn)

I agree with above posters, Hornblower and Sharpe. They may not be big budget but they work really well. Sean Bean is excellent.