ColdFusion or CFML the language is a tool, like any other you might add to your toolkit. As developers I personally feel we choose choose the best tool for the job. That said having another tool available will invariably come in handy down the road rather you write another CFML application or not. General solid programming advice is to try and learn at least one new language a year.
CFML is easy to learn, yet also provides for advanced development, which is why many choose to go with it. I came from a PHP/Perl background and picked it up in a couple weeks. If you are comfortable programming once you get the syntax down you can use to it do anything you can do with PHP. I wrote at length on the comparison in this answer.
Further lengthy Question/Answers to the viability/use of ColdFusion:
Is ColdFusion a good choice for web development?
What is the status of ColdFusion today?
I know you didn't ask about comparisons, you have made your decision. For building Flex/AIR apps with a data back-end imho ColdFusion or BlazeDs is the way to go. ColdFusion allows you to hook up the power of java to serve data with the easy of a scripting language. With that starting point you have your foot in the Java platform which is tremendously powerful and extensive. You can invoke interact with the Java layer and harness that power. Many will make the leap to Java or a more "friendly" JVM language like Groovy or JRuby.
do you guys have any advice on how I can use ColdFusion elsewhere.
slidesix is a recent example of an interesting use of ColdFusion. NASDAQ built Flex/AIR market replay application. Also you can check Ben Forta's site for more sites running ColdFusion to get some ideas.
But I think you already hit the nail on the head with Flex/AIR apps if you plan on making more, much of what Adobe does is work to make integration with their technologies as seamless as possible. Honestly that alone has been what has excited me most about using CFML and the recent addition of open source alternatives in Railo/BlazeDs I have been building Flex apps powered by Railo/BlazeDs without paying a dime to Adobe.
I guess the bottom line is that the Java platform (via CFML) and the Flash Platform (via Flex Framework ) are both not going anywhere any time soon, and for that matter neither is PHP so I think you will have a solid set of skill from which to build on either way you go.