You will love the Jubal Harshaw character in Stranger in a Strange Land (he is a vehicle for Heinlein's philosophy, which is strongly libertarian, but somewhat chauvinistic)
Vernor Vinge has the most original, mind bending sci-fi I have read, and I have read a lot.
Also, you might try some William Gibson, who created the "cyberpunk" genre with Neuromancer. I haven't read all of his stuff, or even Neuromancer, but I like what i have read (Pattern Recognition, Mona Lisa Overdrive)
I am fond of Elizabeth Moon's "Vatta's War" series, and I have bought, but not yet started the Heris Serrano series. The milieu is similar to Joss Whedon's Firefly series. The main characters are engaged in interstellar travel and trade,and the science is largely handwaved rather than explained in detail, but there is more involvement and cooperation with with military operations. The main characters are not overt outlaws, though they are unconventional and run into conflict continually.
And William Shatner's Tekwar is actually not terrible. It's got a Bladerunner-esque dystopian feel with some elements reminiscent of the Matrix (but it predates the Matrix)
And Ender's Game is a classic, but the sequels, while decent, don't quite meet the same standard.
Harry Harrison's Stainless Steel Rat series is a light-hearted romp that is not serious, but it is a hell of a lot of fun. The main character is a con man in god mode.