Yep, Pittsboro is a sweet little town and so is Hillsborough about 20 minutes north of CH. Both are definitely worth a look. I think Orange and Chatham counties both have pretty decent school systems. They just suffer by comparison with the Chapel Hill-Carrboro schools, but it's not like Chapel Hill-Carrboro schools are perfect or anything.
CHC Schools have got their own set of issues—they're very competitive especially in high school and can be very stressful, depending on your kid. I was just reading an article yesterday that was basically saying a "B" student in Chapel Hill-Carrboro schools is an "A" student in most other systems so when the kids graduate their GPAs are actually sometimes a little lower than they would be if they went to a different school — their SAT and ACT scores are higher in comparison. It's that whole Bell curve thing. There is also an achievement gap issue with kids from lower socio-economic backgrounds and some minority groups not performing as well. However even the lower performing groups perform above the state average and the system as a whole always has the highest SAT scores in the state. There's usually at least one kid, and often several kids, in the system with a perfect SAT and/or ACT score.
If you're set on CHC schools, though you'll need to stay in CH/C and be sure you're in Orange County. There are little bits of Chapel Hill that hang over the edge into Durham and Chatham counties and the kids in those areas go to schools in those county systems.