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Adobe Creative Suite (CS) is a software suite of graphic design, video editing, and web development applications developed by Adobe Systems. Each edition consists several Adobe applications, including Photoshop, Acrobat, InDesign, Premiere Pro or After Effects. Photoshop, InDesign, and Illustrator are the industry standard applications for many graphic design positions. CS6 is the last version of the Creative Suite; future versions of their creative software would only be available via their Adobe Creative Cloud subscription service.
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It is a good issue to discuss with and I am sure it would be an unending debate. Avid users of each application will surely defend their reasons why they love the application they are using for they are already accustomed with it.
Each application has its own distinct features that its users liked, so whatever application you gonna used you will be in good hands for both have the same target, i.e. to enhance your digital images.
Considering that you have the latest version of Photoshop, I may suggest to use it and start learning with it. And if in any case you will try to learn the Photopaint, I can assure you that lots of concepts you learned from the Photoshop can be used in Photopaint.
The bottom line here is: Though the application has different approach in enhancing your projects, they have lots in common.
Anyway, I also pasted below the link of Site's fora regarding the same issue. Have a try to read it.
http://photography-on-the.net/forum/showthread.php?t=120889
http://www.nairaland.com/nigeria/topic-4721.0.html
Ed