Best I can tell ? , there in nothing meaningful in the Windows Registry (maybe the key is there, not sure?), but not like any settings that would materially affect program operation.
Otherwise, DC looks to store its settings in %appdata%/Roaming/Digitalvolcano/DuplicateCleaner.
(With DC closed), I'd rename the /DuplicateCleaner/directory to /DuplicateCleaner.OLD/.
Then start DC & see if it will run as expected...
Hmm....
Actually, in the Windows Registry, it stores its settings in a /DC5/ key.
And I'd expect that DC4 would store its settings in a /DC4/ key.
So they are separate.
But... I wonder if DC4 & DC5 aren't looking to both store their settings in %appdata%/Roaming/Digitalvolcano/DuplicateCleaner ?
If so, that would be trouble, I'd think.
So, if you were to rename to /DuplicateCleaner.OLD/, that potentially could also affect your DC4.
Not sure?
Anyhow, you could try it.
Rename.
Open DC5 & see if it works correctly.
(On new open DC5 would recreate the %appdata%/Roaming/Digitalvolcano/DuplicateCleaner directory.)
Or, wait for a mod, who might actually know how it works to respond

.
And with that, it seems the files there are "version numbered" anyhow.
Like, DuplicateCleaner5_Pro_Settings.data - has "5" in its name.
So maybe if there is also a DuplicateCleaner4_Pro_Settings.data - with a 4 in there, you should be OK?
As in, even though the setting are stored in the same location, even though you're using two different versions of DC, they still should not conflict with one another.
So I'd say, worth a try, renaming (as you can always [delete the newly created directory] & rename the .OLD back to /DuplicateCleaner/.
That is if you're comfortable in doing such stuff.