To maximize your experience with your first CSC (or any camera) learn about the basics of photography. Then find which genre you are most interested in and start figuring out which type of equipment you need to start getting the results you want. This is of course simply assuming this is your first camera. If thats not the case then maybe you already know the basics. If you dont, I recommend going to a used book store and finding a cheap old book on photography from the 70's. They can be had for little or nothing and will have tons of useful information. Any camera examples they give will be about old film cameras but this doesnt matter. The basics of photography never change and these old books are treasure troves from the past.
My advice since you have a NEX is to look at using old manual focus lenses from film cameras. I use a NEX 7 and shoot old glass almost exclusively. Its fun, highly rewarding and most times old glass can be had for a fraction of the price of its modern equivalent.
And as kendo said....practice. Practice, practice, practice. You cant practice enough.