Pictou has a nice waterfront area with some great shops and restaurants/pubs, and a walking trail. I am not sure what type of accommodations you are looking for, but there are lots of B&Bs/Inns in Pictou.
New Glasgow also has a nice downtown area, and there is a walking trail that runs along the west side of the river. Accommodations in New Glasgow aren't quite as central to the downtown area as they are in Pictou (wouldn't be walking distance).
You might want to contact the DeCoste Centre in Pictou (www.decostecentre.ca) or Glasgow Square in New Glasgow (www.glasgowsquare.com) to see what upcoming events are scheduled. The DeCoste Centre has a "Summer Sounds" program with evening music, but I am not sure of the dates for it.
Hope that helps some! If you have any other questions, just ask!