Using Raspberry Pi with collection of player piano music and must have custom artwork!
Found the repository for Web art and have verified that using my art using my file names displays my art in the Music > Artists icons.
Is there anything to prevent me from creating my own “Web” directory tree to copy in entirety via WinSCP?
Then I disable “Web Album Art” under Sources > Album Art Settings, correct?
Yes, there are things to prevent this from working consistently or well
but it is marginally functional.
First, the changes do not persist beyond power down/reset. (I am using my own file names for the images to replace those assigned by Volumio.)
Second, images [regularly*] only appear for previously identified artists (via the web).
*At one point all but one of my artist images displayed. I sought perfection–of the moment at least–and was rewarded with never again displaying images for non-identified artists.
Adding a copy of this data to the “personal” sub-directory accomplished nothing save discovering that it is not deleted with the “reset art command.” This is both good and bad I suppose… 
Methinks there’s a bug in the code that’s preventing the “personal” folder from being generated. Perhaps because the data is stored on a USB-connected SSD?
This issue becomes ever more strange. 
I conducted a “factory reset” to find that ALL of the art both “personal” and “web” persisted.
Moreover my art appeared except for the previously unidentified artists.
Previously simply powering on-off found the Music > Artists list complete emptied of icons while the files were present.

I’ll add to that Factory Reset behaviour observation.
I recently had some issues that resulted in me wiping (full format) my USB music drive and copying back the music to it. Volumio “remembered” the old contents, so I did a factory reset, it still “remembered” the old contents.
Now even more bizarro after I let it play for a while. My artwork is now gone.
From everything I came to understand (before use and purchase of premium product) and studied about Volumio, user-defined art should work properly.
Not only that, but multiple genres are not separated as I came to understand before use and purchase.
Something has gone wrong with anything “user” being dumped in favor of web/streaming. This is the exact OPPOSITE of why I chose Volumio!
Success!
All of the files are stored locally and remotely so presuming it’s lost after a restart it [should] be a simple matter of copying either to the \web folder.
I do not believe this should be so difficult. If anything I read about how Volumio behaved in the past is true then this is a new problem.
I much prefer the screen layout on my iPad but I’m not going to spend the time to find out how to capture, save and access a screen shot.
@pwstereo
Did you clean the art cache, before reattaching the drive?
Sources => Reset Album Art Cache
@SwampeastMike
As far as I am aware you can loose the stored album cache when rebooting while the Album art is being populated.
The issue was a partial music library, not with the images.
I moved the artist folders from USB\MUSIC\Artistname to USB\Artistname thinking to shorten the path.
But it went all weird and only had about 20 artists listed, nothing seemed to clear that up.
Since the format and copying back of all the artists, I see the MUSIC thing has reappeared, so it seems like it’s a default of Volumio.