x86 does not require alignment for a lock cmpxchg instruction to be atomic. However, alignment is necessary for good performance.
This should be no surprise, backward compatibility means that software written with a manual from 14 years ago will still run on today’s processors. Modern CPUs even have a performance counter specifically for split-lock detection because it’s so expensive. (The core can’t just hold onto exclusive access to a single cache line for the duration of the operation; it does have to do something like a traditional bus lock).
Why exactly Microsoft documents an alignment requirement is not clear. It’s certainly necessary for supporting RISC architectures, but the specific claim of unpredictable behaviour on multiprocessor x86 might not even be valid. (Unless they mean unpredictable performance, rather than a correctness problem.)
Your guess of applying only to pre-486 systems without lock cmpxchg might be right; a different mechanism would be needed there which might have required some kind of locking around pure loads or pure stores. (Also note that 486 cmpxchg has a different and currently-undocumented opcode (0f a7) from modern cmpxchg (0f b1) which was new with 586 Pentium; Windows might have only used cmpxchg on P5 Pentium and later, I don’t know.) That could maybe explain weirdness on some x86, without implying weirdness on modern x86.
Intel® 64 and IA-32 Architectures Software Developer’s Manual
Volume 3 (3A): System Programming Guide
January 20138.1.2.2 Software Controlled Bus Locking
To explicitly force the LOCK semantics, software can use the LOCK prefix with the following instructions when they are used to modify a memory location. […]
• The exchange instructions (XADD, CMPXCHG, and CMPXCHG8B).
• The LOCK prefix is automatically assumed for XCHG instruction.
• […][…] The integrity of a bus lock is not affected by the alignment of the
memory field. The LOCK semantics are followed for as many bus cycles
as necessary to update the entire operand. However, it is recommend
that locked accesses be aligned on their natural boundaries for better
system performance:• Any boundary for an 8-bit access (locked or otherwise).
• 16-bit boundary for locked word accesses.
• 32-bit boundary for locked doubleword accesses.
• 64-bit boundary for locked quadword accesses.
Fun fact: cmpxchg without a lock prefix is still atomic wrt. context switches, so is usable for multi-threading on a single-core system.
Even misaligned it’s still atomic wrt. interrupts (either completely before or completely after), and only memory reads by other devices (e.g. DMA) could see tearing. But such accesses could also see the separation between load and store, so even if old Windows did use that for a more efficient InterlockedCompareExchange on single-core systems, it still wouldn’t require alignment for correctness, only performance. If this can be used for hardware access, Windows probably wouldn’t do that.
If the library function needed to do a pure load separate from the lock cmpxchg this might make sense, but it doesn’t need to do that. (If not inlined, the 32-bit version would have to load its args from the stack, but that’s private, not access to the shared variable.)