After installing any version of Xcode targeting Intel-based Macs, you should be able to write assembly code. Xcode is a suite of tools, only one of which is the IDE, so you don’t have to use it if you don’t want to. (That said, if there are specific things you find clunky, please file a bug at Apple’s bug reporter – every bug goes to engineering.) Furthermore, installing Xcode will install both the Netwide Assembler (NASM) and the GNU Assembler (GAS); that will let you use whatever assembly syntax you’re most comfortable with.
You’ll also want to take a look at the Compiler & Debugging Guides, because those document the calling conventions used for the various architectures that Mac OS X runs on, as well as how the binary format and the loader work. The IA-32 (x86-32) calling conventions in particular may be slightly different from what you’re used to.
Another thing to keep in mind is that the system call interface on Mac OS X is different from what you might be used to on DOS/Windows, Linux, or the other BSD flavors. System calls aren’t considered a stable API on Mac OS X; instead, you always go through libSystem. That will ensure you’re writing code that’s portable from one release of the OS to the next.
Finally, keep in mind that Mac OS X runs across a pretty wide array of hardware – everything from the 32-bit Core Single through the high-end quad-core Xeon. By coding in assembly you might not be optimizing as much as you think; what’s optimal on one machine may be pessimal on another. Apple regularly measures its compilers and tunes their output with the “-Os” optimization flag to be decent across its line, and there are extensive vector/matrix-processing libraries that you can use to get high performance with hand-tuned CPU-specific implementations.
Going to assembly for fun is great. Going to assembly for speed is not for the faint of heart these days.