It's basically just a matter of building the RSS file and hosting it on an HTTP server. Then you just give users the URL to that feed and they can subsribe in iTunes. Here is a link to the iTunes RSS technical spec: iTunes Podcast RSS Technical Spec There's also an example feed on that page to get you started.
The element that stores the actual location of the files is the enclosure
element. It has a URL attribute which needs to be set to the URL of the MP3.
Example: <enclosure url="http://example.com/podcasts/everything AllAboutEverythingEpisode2.mp3" length="5650889" type="audio/mpeg"/>
All your enclosure elements will just need to point to the proper place in Amazon S3.