You can place your xml and mp3 files wherever you want within your domain structure. For example, if you have all of your mp3s in a folder named 'mp3' the URL will be: example.com/mp3. You will just need to be sure you give that specific URL to itunes.
It seems the XML can be placed anywhere as well. It is normal to either place it in the root directory for your website or under an appropriately named folder such as 'podcast'.
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