I have a two TwinStore set up here and would also be interested to know how Sooloos handles the situation. Theoretically it will look for drive space and use what is available i.e. fill up TwinStore 1 before going to 2.
However I'm not convinced that is what is happening here. At first I filled up no 1 with more than 5000 then it auto went to no 2. BUT since then I've deleted some files in the first TwinStore & it seems all new rips are going into no 2 leaving space in no 1.
I guess the only way you will be able to do what you want is to backup all from your present TwinStore, disconnect it, then connect the next unit & restore all the files to it. You can then replace the present drives with 3 TB units and use it again. I would advise care about formatting your present 2 TB HDDs until quite sure all has been restored properly on your new 3 TB unit.
Good luck - what you are planning will take a few days to achieve. I'm also running out of space but am acquiring another (used) TwinStore so I'll be running 3 of them to have a total of the 6 TB capacity you are planning.
Sooloos sort of keeps us busy (and poor) doesn't it?

John