Unless you're a hardcore CLI junkie, you should probably start with something like PC-BSD: a user-oriented derivative of FreeBSD. Once you get comfortable with the differences between BSD and Linux, check out FreeBSD, OpenBSD, or NetBSD. FreeBSD is a performance-geared OS that is very nimble, OpenBSD is a stability/security driven OS, and I can't say much for NetBSD because I don't use it (other than to say NetBSD has been ported to tons of architectures).
And even though the BSD's all derive from a common codebase, they've diverged enough to be truly different operating systems. Coming from Linux, you'll likely notice that the BSD's are more consistent as well, because they are developed as kernel + userland by the same team, not kernel by one team and userland by another.
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