Yes, I can tell accents from various states in the south apart. It's funny that you brought up "Sweet Home Alabama," because my roommate and I went to go see it when it was at the theatres. We said the exact same thing that your friend did.
The easiest to pick out for me are Alabamaians. People from Alabama pronounce things with a flat "i". I can't really think of how to explain it in text, but it's like pronouncing anything with the letter i by just lowering your jaw.
I pick up accents very easily, so I guess it is easier for me to tell them apart, too.
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