I finally took a deeper dive into the 6738 docs to look at some of the details you're concerned about.
First the spec sheet declares pretty clearly that the output signal has 16-bit resolution. Any other digital signals needed for reference selection, polarity, whatever would be separate from the fact that you will get 16 bits worth of resolution from the DAC conversion.
I saw the part of the manual where each DAC supports 4 AO channels, which was a surprise to me. Further reading about timing signals didn't seem to clarify how this sharing works. I expected to find something analogous to the AI Convert Clock that's used to multiplex analog input conversions into a shared ADC on many common NI multifunction boards. But I didn't see anything like that in the manual nor did I see anything similar in code under a DAQmx Timing property node.
So I can't give you a final, authoritative answer about the details of how it works, but the description and specs seem pretty clear that there are no special restrictions about which channels can be used simultaneously. So I personally feel confident that you can generate on all 32 channels, I just don't know precisely how those DACs get shared in the process.
-Kevin P
ALERT! LabVIEW's subscription-only policy came to an end (finally!). Unfortunately, pricing favors the captured and committed over new adopters -- so tread carefully.