What is the best way to travel from Salzburg (or Hallstatt) to Florence, Italy ? Train or plane?
Not the best options anyway. With train in most cases you have two changes - Innsbruck and Verona or Bologna. With a plane you have to go to Munich first as the Salzburg airport does not offer viable options. Even by car I usually need eight full hours. From Halstatt add two or three hours. From Halstatt you could also consider going to Vienna and then by plane, but probably Munich has more frequent flights.
Over twenty years ago, we took the train from Munich to Florence, with no changing. Not sure if the train went through Salzburg or not. Check the internet for the train. Driving can encounter traffic going into Italy.
There is a single direct train between Munich and Florence, and is a night train arriving in Florence very early in the morning. Still one change necessary, as it does not travel over Salzburg. Timetables on the oebb and db web sites.