RGSS(1,2,3,...n) have thus far been a gaming API implemented via the Ruby language by Enterbrain for use in their RPG Maker products. It extends Ruby to deal with gaming concepts, but restricts and changes Ruby in several aspects, as to keep the internal system(s) like Audio, Tilemap, etc under lock and key (closed-source), and to reduce type-type (for instance, rooting all directory and file classes to the project directory).
Basically RGSS is a collection of code implemented in the Ruby language, aka an API or foundation for developers to work with, instead of having to do it themselves (read reinventing the wheel...for this usecase at least).
Sooo, the difference is that Ruby is an actual programming language, whereas RGSS is a collection, or codebase written (mostly) in said language. While you can have just Ruby, you can't have just RGSS without Ruby. As for your reason behind this question, learning only what is 'necessary' to get by creating your game isn't exactly the best way to go about things. I would highly recommend learning Ruby as it is, then extending your knowledge with RGSS(insert number here). That way, all the concepts are oriented around your knowledge of Ruby, making you a more robust and adept code developer.