After I did the Grossglöckner (staying at Hotel Mölltaler), I took the Plöckenpass south into Italy. Stopped for a gelato in Tolmezzo, then took SS52 (not the autovia!) east as far as Chiusaforte, then SP76/SS54 across the Slovenian border. Down to Bovec, and turned off to take the Vrsic Pass south-to-north. Spent the night at Kransjka Gora, next day continued to Lake Bled and Vintgar Gorge. From there I went to Maribor and back north into Austria, but it is also perfectly nice to follow the Soca river valley all the way down to Gorizia.
Then either head up into the foothills or shortcut across the Udine plains back into the mountains via Trento, check out Lago di Garda, and keep going west for long enough that you can get up to Bormio and approach the Stelvio Pass from the west. I would recommend cutting north into Switzerland from there - the eastern side of Stelvio is an absolute kick in the nuts despite the dramatic views - and check out Liechtenstein on your way back into Austria and the Bodensee coast. You can stop at Castle Neuschwannstein on the way back to Munich (great for selfies on the outside, apparently not worth the inside entry ticket).
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