There is a relatively new train directly to Venice from Munich.
For baked goods in Munich, Hofpfisterei is a good standard for Brezen or bread.
As others said you can reach many areas of Europe within a day. In Germany you could reach every pcket as well (Berlin has a 5 hour train connection). So it depends what you would like to explore. For a light hike/nature there is the Bayerischer Wald for example.