"What are the best places to focus on in a couple days when based in G-P?
I assume you narrowed your choices to G-P and Salzburg because you have researched those areas and were attracted by certain sights and places in the immediate area. What's best depends on your interests, which are...? Which places are tugging at your sleeve? You could spend some time in both, or the whole week in one place if your interests match up better with just one.
Are there areas in this part of Austria (Salzburg) that are more worth spending time in vs those around G-P (eg, Hallstatt)?
Hallstatt is picture-perfect but won't demand much of your time. Much closer to Salzburg are Werfen and Hohenwerfen Castle. Into cars? What about the Porsche Museum? Then there's the Eisreisenwelt. Have you looked into those? These Austrian options are all quite different from what you'll find in G-P. Not sure how you would compare. Then of course there's Berchtesgaden and more just across the border.
In between Munich and Salzburg is the impressive Herrenchiemsee Palace (on an island in the lake of the same name) which might interest you.
https://www.breitbrunn.com/Fotos/Breitbrunn-Luftbild.jpg
https://www.schloesser.bayern.de/englisch/palace/objects/hch_ns.htm
And right near there in Aschau you can catch a lift up to the Kampenwand peaks for a view and some hiking.
https://kampenwand.de/index.php?rex_resize=835h__panoramakarte_sommer.jpg
http://www.chiemgau-wandern.de/images/pictures/w7de111120b2b000893989862a46d7f3/w7e081210161900025609dcff1eea1a3/Sonnenalm-%281-von-1%29.jpg
http://q-ec.bstatic.com/images/hotel/840x460/439/43953086.jpg
In between Munich and G-P you might enjoy a visit to the medieval town of Landsberg.
Landsberg photos (scroll down) - https://www.stadtbild-deutschland.org/forum/index.php?thread/1974-landsberg-am-lech-galerie/&s=d2aacc2f01314ce15f5fed3ae6cfec94df76ba83
https://www.tripadvisor.com/Attractions-g641965-Activities-Landsberg_am_Lech_Upper_Bavaria_Bavaria.html
Andechs Monastery (and brewery) is covered in Rick Steves and is just a ways outside Munich and also on the way to G-P.
I don't think most people with a week would find room for a visit to Venice.