I'm from Charlottetown. I love it here! Just got back from Disney World and we were talking to the cab driver about how much we all love to go away (my sister, who is married with three children, her single sister in law and myself) but how nice it is to come home. We all agreed it's one of the best places to live. (Well, we probably said the best but I would not want to insult anyone!

)
As far as schools go, we have some really great teachers and some wonderful schools. Everyone will have an opinion and it usually just involves their own schools. If they liked school, theirs was the best, and their rivals were the worst. If they didn't, they'll tell you to stay away from their school. I would say that each school around has some great qualities and probably a few things to work on as well.
I love all of PEI, but I like the convenience of living in Charlottetown. I have worked in some smaller communities and also lived in some litte towns as well, and I liked them, but I guess I like living here. Not downtown but in the 'burbs.
Good luck with your decision.