I live in the Raleigh area. I have lived in NC most of my life--rural NC (10 miles to town), semi-urban NC (Charlotte), and suburban NC (Raleigh/Cary). I like the weather almost everywhere in the state. This area (Raleigh) is probably the most diverse in the state, has above average good schools, various good-paying jobs, and bike accessibility to everything I would want regularly--work, errands, recreation, festivals, etc.
I've been to Greenville several times, have a couple friends there, and know a couple families with children at ECU. I wouldn't move there from here, but I can't think of anywhere in NC I'd rather live than where I am. Greenville might work out much better for you. If you might be uncomfortable with towns < 100K, then you'll want to go somewhere else. Also, Greenville puts you about 1.5 hours closer to the coast than Raleigh (and 1.5 hours further from the mountains). I prefer the mountains over the coast, so I already have 3 hours to drive to get to the trailhead. I wouldn't want to add another 1.5 hours to the trip.
As to NC culture, from my experience here, higher populations are more likely to fit your profile, lower populations more likely to favor conservatives. The college population will preserve some leftist presence in town, but the general population will tend to be a bit more conservative than some of the other NC cities with more folks from other states. Greenville might be a place people would be from (no choice in where you're born), but it would not likely be a place people would choose to move to .