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The claustrophobic atmosphere of The Carhullan Army/Daughters of the North reminds me of Jacqueline Carey's Santa Olivia, which has militaristic overtones and an interesting heroine. Again, not very science-y, though.
Kris Longknife is a series that I have a hard time taking seriously, but still read each new book that comes out and wait for the next one.
Bitter angels is a book that I had a really hard time getting into, even though it is written by an author I really like--Sarah Zettle under another name.
All in all the Tanya Huff Valor series and Karen Traviss books are my favorites.
Anyway, I second Elizabeth Moons books.
Also second (or third, or whatever) On basilisk station :)
Edit to fix touchstones
Sirantha Jax series by Ann Aguirre. again, not strictly military science fiction. mc is a member of the corps, a jump pilot, who crashes, loses her memory and is than recruited to overthrow the existing order.