Well, after a lengthy backup session & tinkering over the long holiday weekend, the transition is now complete. Everything seems to be up and running, though I've not yet had a chance to tinker around with benefits of btrfs vs a standard raid 5. Here are some of the commands which came in handy during this process, to avoid any issues with OMV, I recommend you remove the file system from OMV first and wipe the Disk as if you are going to be using a WebUI to make a new raid / fs.
parted /dev/sdx mklabel gpt
parted -a optimal /dev/sdx mkpart logical 0% 40%
parted -a optimal /dev/sdx mkpart logical ext4 40% 100%
mkfs.ext4 -L xyz /dev/sdx2
Replace "/dev/sdx" with device path as seen on the Disks tab. I've used 40/60 split for my setup, in this case using the slower 60% partition as a standard ext4 partition. Replace "xyz" with the label you wish to see within the OMV, unfortunately you will not see the partition unless you first format it via CLI, but after that you'll be able to mount it using WebUI. Sitenote: this disks will mount using uuid instead of their label, path will be /srv/dev-disk-by-uuid-####/, not sure how to force it to mount using the label, but we'll be using unionfs anyways, so not a big deal...
I will not go into details on how to use union filesystems plugin (I'm sure it's discussed at length elsewhere within the forum), but the partitions will showup as if they were full drives, so no need to go folder by folder. (mergerfsfolders is not needed in this case). In my case, my only deviation from the defaults was the use of "Most free space" policy and addition of ",cache.statfs=1800" to cache the "free space" calculation for about a half hour. I do so to prevent frequent disk switching when writing multiple files to the drives when they are about evenly full.
As per a good starting point forom doscott Btrfs raid can then be created using this command:
mkfs.btrfs -L raid5 -m raid5 -d raid5 /dev/sdx1 /dev/sdy1 /dev/sdz1
I've labeled mine as "raid5", but you may be using something different. If using two drives in stead of three, use raid 1 (diplication), otherwise replace "/dev/sd?#" with path & partition numbers you were going to use, in my case I've used the faster 1st partition.
After the filesystem is created, it can be found & mounted via filesystems tab within WebUI. It will actually mount as "/srv/dev-disk-by-label-????", so the label is useful besides within the WebUI.
Attached is the end result, restore is still in progress, so usage data is off, but everything is seemingly working well