iTunes match invokes the 90 day Apple id rule, so in answer to the question you cannot use 2 iTunes match accounts on one computer unless you are willing to wait the 90 days.
Note that the 90 day rule applies to the computer as a whole, not OS X user accounts - so even if you create another user account on your iMac for the 2nd iTunes library you still cannot activate iTunes match on that account.
I use a VM to manage my 2 seperate iTunes match accounts.