Sorry, I don't know since I don't use TM....besides TM backups stored on a NAS may be a bit different than a TM backup stored on a locally connected external drive. From reading these forums, it doesn't appear like you can copy a TM local backup drive, but I believe it may be possible for a TM backup on a NAS.
I wouldn't touch your current backups. Did the new share work for you Macbook? I would say experiment with the Macbook by creating yet another new share to experiment test things out before trying to modify the iMac's backups. This includes trying to have two TM backups on two separate shares and also trying to move an existing backup to another share.
I would think if you added a new share, then you should be able to add it as a second backup destination, but then I don't know how TM handles backups to networked locations (it is possible to add a second local TM backup drive to have two TM backup drives).
Hopefully another contributor with more knowledge of TM and TM backups to a NAS will chime in here.