self,
I'd suggest having a look at a few guidebooks covering the regions you want to visit. Those will provide information both on towns that may be of interest to you, as well as transportation to reach those towns. As you're "comparitevely new to Europe", it would be helpful to read Europe Through The Back Door prior to your trip, as that has a lot of good information on "how" to travel well in Europe.
It would help to have a bit more information on your circumstances. For example, where are you travelling from, how long are you planning to stay in Europe (you mention that you are "Not intending to live in big cities"), what type of accommodations you prefer, etc.