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welcome to the flex forum. i have been using flex for a little over a year. though i must say it has been one of the must frustuating languages i have encountered , i must also mentioned is also one the the most rewarding. Specially at the job place when you show off something really unique and people are wondering whoooa how did he do that. Ok enough i'll get off my soap box. what you are trying to accomplish seems to me very doable in flex. there are so many ways to acomplish things in programming that it would be a crime if i only talk to you about one way. One thing that help me a bundle is keeping an eye out in this forum. When questions come up ask yourself how would i acomplish that same task. Also keep an eye out for answers to question that you otherwise would have no idea to tackle. There are alot of slick people in this forum, and they will be able to point you in the right direction when you get stuck.
I will encourage you to look into cairgorm, degraffa, and must importanlty actionscript 3. In my opinion anything really cool does not happen in XML but in actionscript. Just my opinion thought. Good luck in your journey it has been a rewarding one for me.
Depending what you want to do specifically, you'll also benefit from learning / using some server side technology. Most Flex Apps focus on User Interface, while using a database for data storage and an application server as the middleware to pass info to and from the databaseand the UI. ColdFusion comes from Adobe, is easy to learn, and is my preference. PHP is anohter common one. .NET and/or Java are big in Enterprises.