Re: "UPS backing up a UPS" -- This is a bad idea, but harmonics is NOT the main reason why it's a bad idea. The reason is that redundant devices in series REDUCE reliability, whereas redundant devices in parallel INCREASE reliability. If you wanted to use two UPS systems to increase reliability, I'd suggest investigating if the PLC could be purchased with dual power supplies, and source each power supply from a separate PLC. If that's not possible, I'd investigate a fast-transfer switch to select between UPS systems. I'd go with only one UPS before plugging one into the other.
Redundant UPS systems are probably overkill, though, for most PLC applications -- as previously mentioned, you've lost your process anyway. A cheapo UPS will keep your data logging going most of the time, and if that drops out every 5 or 10 years you can probably live with it (but maybe not).
One big UPS will fail less often than several small UPS modules, assuming they all have the same MTBF. Actually, large systems usually have lower MTBF numbers, which makes the single-module solution even more attractive. Assume for now, that all UPS systems have MTBF ratings of 200,000 hours -- therefore, as there's 8760 hours in a year, you'd expect a single-module system to fail, on average, every 22.8 years. However, if you're using four modules, you'll have modules failing four times as often -- that means one out of the four UPS systems will fail, on average, 22.8/4 = 5.7 years.
All that aside, I agree, go with the pure DC system if possible -- it's not clear to me if it is possible in your situation, given the I/O requirements, but that's already been discussed.