Hi Nick,
It would appear that the Z8S180 that will not multiply the clock is a Z8S180 Rev. K. The Rev. K does not have the clock multiplier capability. The register will always read 0xFF no matter what order it is written to. Your other Z8S180 that does achieve 33MHz must be a Rev. N which does support the clock multiply bit.
Sadly, the revision of the Z8S180 is basically not marked on the chip at all. Additionally, suppliers do not understand this nor show it in the part specs.
If you are using RomWBW, you will see either Z8S180-K or Z8S180-N listed in the initial boot message which indicates which chip variant you have.
I am attaching a tech note from Zilog that specifies the differences in the revisions.
-Wayne