I have now tried to use this technique in a test case. It generally works, but could be improved. Details...
TEST 1: I made a POI. I placed 4 "Loot T1" Parts in different locations. Gave them all the same GroupName of "loot." Set the probability of each to 20%.
Results: I observed 5 different outcomes. I either saw 1 of the 4 picked and placed or I saw none of the 4 picked. This makes sense, as the combined probability of placement for 4 Parts at 20% probability represent a combined probability of 1.0 - (1.0-0.2) ^ 4 = 0.5904 or 59.04%. Thus there was approximately a 40% of none of the parts being picked.
TEST 2: I modified TEST 1 so that the probabilities were 20%, 20%, 20% and 99%. The idea being that the 4th choice would always get picked if the first 3 were not.
Results: This worked as I did not see any results where none of the Parts were placed. However, the 4th choice (with 99%) was picked most of the time, which makes sense.
TEST 3: I attempted to tweak the percentages such that all 4 Parts might have roughly the same percentage of placement. To do this, I needed to pick a percentage for the first 3 Parts that would leave roughly that same percentage for the 4th Part even though I had to set the fourth part to 99%. I ultimately settled on 30%, 30%, 30%, 99% because 1.0 - (1.0-0.3) ^ 3 = 0.657 or 65.7%. That left a 100% - 65.7% = 34.3% chance of the last Part being picked.
Results: While I did not see a case where none of the Parts were picked, I still saw the majority of the time the 4th Part was picked, rather than a more-even distribution.
Conclusion: Since we're dealing with probabilities, it is possible TEST 3 really could lead to more-even distributions. More testing would be needed to see that. Still I suspect POI designers are not likely to want to go through the probability mathematics to balance out the odds of even placement. While configuring Parts, the Probability slider has 20%, 40%, 60%, 80%, and 100% as easy stops. You can select any probability by clicking in the track. (Click-Drag in the probability slider produces NREs.)