"She talks as she walks" is correct, as I assert! It is also a proverb meaning "She gives as little thought to what she says as she does to how she goes along." Used when someone has made an embarrassing or (unintendedly) offensive remark.
What's the difference between Ela anda and Ela caminha?
Silly question...but is this sentence discussing 2 women?
If one woman would it be "Ela fala enquanto camninha"?
No, this sentence is discussing only one woman. The pronoun "ela" only was repeated two times on this sentence.