If you're more specific I might be able to help you. First of all what type of users are you trying to enumerate? I assume you want Windows users? This isn't specific to Cain but Metapsloit has a more up-to-date tool that you can use to enumerate users over a network. You might want to first think about this though:
-How does a computer enumerate users? It is one thing to click a button but what is that button doing? Most tools responsible for remote user enumeration leverage the SMB protocol that frequently runs on port 445. Are those ports open on the computer you're targeting? If not, there's a strong chance your tool won't be able to enumerate users. Reading some of this might help:
http://en.wikipedia.org/wiki/Server_Message_Block-As for solving the problem; I can't point you in the right direction as far as Cain goes but I do like the metasploit modules:
auxiliary/scanner/smb/smb_enumusers