Unfortunately, I am only familiar with the MP5.1. However, it might be similar because Greg did a lot of 5.1 videos as well. In the 5.1 PCIe world, the only reason to upgrade from a regular SSD in those SATA bays to NVME is the addition of speed. Because of that everyone uses the fastest PCIe slot #2 in the 5.1. Otherwise the upgrade would just add another SSD with no real speed benefit. So to answer your questions, - if your upgrade is about to get a speedier SSD, you will need to use the fastest slot available.
Now, when it comes to SSD NVME speed, you will have some speed benefit to use a sigle NVME blade in your fastest slot. However, those slots are very old and don't offer that much of a speed boost. Because of that, the industry invented the method of a PCIe bridge card to use the bandwidth of two slots into one to gain double bandwidth with only one slot. Since I have my 5.1 for more than 8 years now, I did use every SSD Generation there is including the older AHCI M2 blades, the predecessor of NVMe. For your MP3.1, most likely your slots are slower compared to the 5.1 slots. If that educated guess is correct, a more expensive dual bridge card may not make much sense because of limiting slot bandwidth in your 3.1. - but a less expensive single slot NVME card may make a lot of sense.
If you can get the OWC Accelsior real cheap on eBay, sure go for it. Otherwise, there are many good single cards you can use. It really comes down to space availability in your tower and the maybe bulky cards above and beneath.
I use two of those high speed dual slot bridge cards and one single card. My fastest boot NVME is in the red dual slot Ablecon card for maximum boot up time. I do sometimes switch around cards and I absolutely feel the speed difference in newer MacOS revisions. It seems to me that newer software apps are programed on the premisses to have certain PCIe bandwidth compared to older MacOS versions.
By the way, My humble respect for your outstanding photography projects on your homepage. Great, stunning pictures that tell a story.