¿Son ustedes de Chile?

English Translation

Are you from Chile?

Uds. son de Chile? Would this also be correct, and would it mean the exact same thing?

Yes. Meaning-wise, it’s the same.
The difference, if there were to be any, would be in the stressed information. They can both be neutral, but I’d say I’d use your word order if what surprised me was they of all people were from Chile.
Actually, maybe something similar to:
“Are you from Chile?” vs “YOU are from Chile?”