Update: Because people are still finding this answer, I feel like I should provide a suitable update. By now, I hope it's clear that Clang is absolutely the way to go when programming, with Clang being the default compiler in the newer versions of Xcode and supporting ARC and new and upcoming language constructs (array and dictionary subscripting, literals, etc.). There's almost absolutely no reason to compile with GCC anymore, and for codebases using ARC and new features, using plain GCC is no longer relevant or possible (LLVM-GCC may support these features, but it provides no advantage over Clang now that Clang is completely stable).
By now (with LLVM-2.0 included in the Xcode 4.0 beta), LLVM is mature enough for production code use. It compiles a little quicker than GCC, and produces faster code, so use it whenever you can (pretty much, try to avoid GCC if something better is available). The standard Xcode 3.2.5 install contains LLVM-1.6 (not the latest), so I'd recommend either running some speed tests to see if there's a noticeable difference between GCC and LLVM, or compiling Clang from source and getting the latest version.
Essentially, there's no need for GCC any more, LLVM + Clang is more than enough.