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As stated in my comment, doing this with =importXML and XPath seems tricky.

But doing it programmatically, using the XmlService of Google Apps Script, looks easier.

I have written the following:

function parseTvRageXml(url) {
   var result = [];
   var xml = UrlFetchApp.fetch(url).getContentText();
   var document = XmlService.parse(xml);
   var root = document.getRootElement();
   var atom = XmlService.getNamespace('http://www.w3.org/2005/Atom');
 
   var show = document.getRootElement();
   var episodeList = show.getChild("Episodelist");
   var seasons = episodeList.getChildren("Season");
   for (var i = 0; i < seasons.length; i++) {
     var season = seasons[i];
     var seasonNum = season.getAttribute("no").getValue();
     var episodes = season.getChildren("episode");
     for (var j = 0; j < episodes.length; j++) {
       var episode = episodes[j];
       var resultRow = [];
       resultRow.push(seasonNum);
       resultRow.push(episode.getChild("epnum").getText());
       resultRow.push(episode.getChild("seasonnum").getText());
       resultRow.push(episode.getChild("airdate").getText());
       resultRow.push(episode.getChild("link").getText());
       resultRow.push(episode.getChild("title").getText());
       result.push(resultRow);                
     }
   }
  return result;
 }

In effect, it fetches the content from the given URL, parses it as XML, and iterates through the elements, extracting values of the elements you wanted, which is stored in a 3D array (result), and returned.

To use this, you must install the script in your spreadsheet. Click the Tools menu → Script editor, and paste the code listed above. Save the script.

In the cell where you want the output, enter

=parseTvRageXml("http://services.tvrage.com/feeds/episode_list.php?sid=3183")

The result should be a list of episodes, with the following columns:

Season number | epnum | seasonnum | airdate | link | title

I have set up an example spreadsheet to demonstrate this, feel free to copy it.