You can set up W32TIME in any way you want. Normally, you'd set up a three-tierd system.
1) At least one Primary Time Server that pulls from a well-defined time source (list of those is publicly available and I believe also listed in W32TIME documentation)
2) At least one Secondary Time Server which pulls time from local Primary Time Server
3) Workstations pull from Secondary Time Server
In order to make this setup work, you will need to modify W32TIME.INI accoridng to the documentation.
Of course you could use the Samba Server as time source for the W32TIME server. I have found W32TIME to be very reliable.
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