Good starting game?

Once one understands the warring mechanics, there isn't a lot to master ; the game is very limited in scope (that mean when compared whith other Paradox games. In Hearts of Iron for example, there are the planet-sized playground (increasing the logistical problems and the need for careful planning), the resources (like petroleum) to control..

Also yes there is a Napoléon avatar somewhere in the pages, you must have overlooked him.

I found Austria to be the best starting country. Two of your worst enemies start off at one another's throats (Russia and France do not like each other) and often stay that way for a long period of time, and your other two enemies (Prussia and the Ottoman Empire) just aren't as good. Prussia is smaller and can be overpowered, and the Ottomans are a paper tiger that crumples like...

like...

...well, like a tiger made of paper.

This leaves Austria with two easily beatable enemies in the early game, while you're learning the ropes, followed by two very difficult foes to beat in the late game using all you've learned. (France is a technologically advanced nightmare, while Russia is just very very very big and has a very large army).