Yes, the Assign command with the ADD keyword will work in this case, but as Piru said, it needs to be supported by the application trying to access devs:whatever. IIRC VNC supports this as an option you can enable (TrueMultiAssigns I think), then typing dir devs: will list all the files. But as ramlib supports multiassigns, it will search all assigned paths when any application actually tries to open a file in DEVS: through the normal methods. Beware though, it will stop looking when it finds the first version, not the newest version, so if you have a copy in both locations, it'll only use the one in SYS:Devs/ and not the one in SYS:MyDevs/.
If you only want to use SYS:MyDevs/ as your Devs drawer (though I can't think why you'd do that), you can use "Assign DEVS: DISMOUNT" and then "Assign DEVS: WB2:MyDevs" to reassign it.