I started out as a Corel user and didn't get started with Photoshop until version 6. Now I know I would probably never want to go back. Although there is a learning curve, there are so many resources that can teach you what you need to know quickly. Just as 2436mm says*" The best way to learn is by just playing around with the tools and functions"*, is a very good start. Also all PS comes with a getting started guide built right in.

Good luck to you. :)