Any number of the "military presidents" qualify---Andrew Jackson,Zachary Taylor, Ulysses Grant, Ike (one has to consider Washington a "military president" as well). I suspect there were civilians in there too.
Andrew Jackson served both as representative and as senator in the US Congress.
I had forgotten about Taylor; he only served 16 months. The funny thing about Taylor is that he never even had VOTED! I should not have forgotten about Hoover. But it is interesting to note that the three Republicans who harmed the party the most politically all lacked prior office.
(No, I don't count Nixon in that list. Although the GOP lost 4 senate seats and the Presidency, they came right back in 1980 with the Reagan Revolution.)
IIRC Herbert Hoover was never elected to any office prior to becoming POTUS. He gained his fame through running a massive famine relief project (or something like that) in Europe after WWI.