Kryssa: welcome to the wonderful world of quilting where everyone has a different way of doing things!! You'll probably get a lot of opinions from us on what we prefer. The more you quilt the more you'll develope your own ways.
As for me, I don't pin individual pieces together-I just lay them on top of one another. When I am matching blocks at seam intersections I always pin before and after the seam--just remember to remove the pins when you get to them and don't sew over them! (Ask me how I know this LOL)
The thing that has really helped me get (almost) perfect 1/4" seams is the 1/4" foot for my machine and practice, practice, practice.
These are just my humble suggestions--try different methods and stick with what works for you. And Good Luck!!