Note -- This is all from EU3, your mileage may vary in EU4 but I'd bet these countries are still worth trying:
- Holland is great once you form the Netherlands; you start off as a vassal but in this case that's good, break your alliance with Hainaut immediately and you'll (probably) have a good 15 years of peace to build up a power base through trade. A reasonable goal with EU3's 1399 start is to form the Netherlands and annex all of your core provinces by 1500. From there you can basically do what you want, I tend to favor colonizing the rich overseas areas (Caribbean, Indonesia).
- Burgundy is good if you want to just conquer things right off the bat, because you get a half dozen or so missions which let you get to the Duchy's historical apex. After that you're in good position to get elected Holy Roman Emperor and/or conquer France (whether through out-and-out war or attempting to marry into France).
- Castille probably has the most fun 1399 start because Aragon starts without an heir; an alliance with Portugal and efficient resource management can net you both Granada and Aragon in a few years. I managed to form Spain in 1403 and, through some really good luck, inherited Portugal by 1410 as well. It gets really dull after that though because you're typically waiting for colonization range to increase, fighting over useless territory in North Africa or getting dragged into stupid wars with France & Friends.
- England's also a fun start since you get the Hundred Years' War missions and unification missions to distract you while you wait for colonization.
After you've got some experience under your belt and you're ready for a tougher challenge, the most rewarding country in the game is Byzantium. A 1399 start leaves you with the southernmost tip of Greece and Constantinople itself as your only lands; by 1500 you can be the master of the Balkans, conqueror of the Ottomans and Egypt and fighting -- and winning! -- against the various hordes in Eastern Europe and Southwest Asia. Probably my most fun game ever was a Byzantine run where, by game's end, I had conquered the Roman Empire, disbanded the Holy Roman Empire (and then conquered its constituent states), colonized Ukraine from the Golden Horde and expanded through Persia into India. You could move from Portugal to Bangladesh and never leave my borders.
If you want an interesting faction, the Byzantines are definitely it.
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