If you use podPress to add podcast episodes then only as part of an article. An episode will not be a part of the content but something like an attachment of a post. podPress can show a player or a link at the beginning or the end of the posts content (If you don't write something into the post editor then there will be e.g. only the post heading and the player on the blog page.). You can choose on the "General Settings"- and "Player Settings"-page of podPress how the episodes should appear at the posts.
There are at least 2 ways to upload and store your podcast episodes:
You can upload the episodes with the WP media uploader (the buttons above the post editor). The file will be stored as all the other images and media files automatically. After the upload you copy the complete URL of the media file and paste it into the "Location" field at the "Podcasting" box below the editor frame.
The other way is that you decide to use one specific folder on the server to keep all podcast episodes. To do that you have to specify the folder name at the "Local path to media files directory" field on the "General Settings"-page. For the upload you have to use an FTP client. All media files which are uploaded to this folder will be listed by podPress in a select box at the "Location" field at the "Podcasting" box below the editor and you can simply select the file.
Of course you can upload the media files via FTP to the usual upload folders, too without using the option "Local path to media files directory" (Then you would have to specify the URL in the "Location" field manually).
In general: if you upload the files via FTP without the WP media uploader the files will not be listed in the media library of your blog (and these files are not getting a WP attachment ID automatically).
podPress adds the podcast elements to the regular RSS feed and creates a new RSS feed which contains only the podcast posts with their audio/video files. This feed has the address e.g. http://www.example.com/?feed=podcast or http://www.example.com/feed/podcast.
With podPress all RSS feeds contain the news feed elements which are necessary for iTunes and probably for other podcast client software, too.
If you want to have a feed without the podcast posts then you could set up a further RSS feed which does not include these posts or to exclude posts of a certain category from the feed. There many ways to do that.
One way is to use the built-in RSS widget of WP. There you can input a custom feed URL and the blog visitors can subscribe to it by simply clicking on the new icon in the sidebar of the blog. The custom feed URL should look like this
http://www.example.com/feed/?cat=-4. In this example 4 is the ID of the category of the podcast posts and the minus excludes this category.
But there are several plugins which make it probably easier to exclude categories from the all the feeds (search for "exclude" in the plugin repository).