For PPL I know a great one in Madrid LECU. It's not a big school, but his owners (the instructors) are very experienced pilots that have been flying all their lifes. They put all the effort on the students, and they are always very attentive (literally, you can always call them or take extra lessons). It's there where you really learn to fly!
The problem with big schools here in Spain its that they put all their focus in the integrated ATPL courses. And they usually have instructors with not much flying expreience. That being said, some have pretty good ground schools.