I'm a west-coast hiker and have no direct experience in your neck of the woods.

To help get you started planning, there is plenty of information available out there regarding the Appalachian Trail and it may be your best option for walking the majority of the distance you are planning to cover. The best source on the web for the AT would be whiteblaze.net.

Road walking is a very different beast from trail hiking and I have no experience there. I'd anticipate that sticking to back roads or rural state highways as much as possible would be the best approach.