Check out Vernazza in Italy. It's one of 5 little towns in a row in Cinque Terre on the Italian Riviera. Awesome place that I had never heard of before - a friend recommended it and it was one of the highlights of our trip to Europe almost 5 years ago.
http://www.cinqueterreonline.com/
Since you are already going to Munich, then spend a day at Dachau - the original concentration camp. It's a short trip on the S-Bahn from Munich. Also, go to Neuchwanstein Castle which is in Fussen - about an hour away by train. Also recommend the bike tour through the countryside as well. They take you to Swan Lake (the swans are mean little buggers) and a fun run down a slide for a pit stop.