If you are used to PSP then the way photoshop CC works will be somewhat familiar but very different. If you don't like learning by reading then I suggest going to Adobe TV. There you will find instructional videos on everything you might want to know and be able to do with both Lightroom 5 and Photoshop CC. Take your time it will seem a tad complex at first but once you understand the basics then it will get much easier. I use Photoshop much more than I do Lightroom only for the factor of I started using it along with PSP many years ago, finally setting PSP aside as I learned things were so much easier and better in Photoshop.
Getting Started with Adobe Photoshop Lightroom 5 | Adobe TV Products | Lightroom | Adobe TV Learn Photoshop CC | Adobe TV
I suggest looking for and studying the basics first