Can't send email from one specific .mac account

I have two .mac accounts on three different machines. My main email account gives me "cant send with server smtp message..." use a different server. I can send just fine with my other .mac acct on the same machine. But I can't send from my main .mac acct on any of the machines or the web client at home or work. I have created a new user from scratch and set up the .mac acct on it and still get the errors. So it doesn't seem to be a problem specific to machine, user, or network. Any suggestions would be greatly appreciated.
Thanks
iMac intel   Mac OS X (10.4.6)  

In your Account setup (via Mail Preferences) you may have to set up an Outgoing Mail Server (SMTP) entry. As an example I have a IMAP account and a POP account. The IMAP account has the server smtp.<imap_domain>.com and the POP account has mail.<pop_domain>.net.au. I also have other domain entries which come into play if I am visiting friends or colleagues and need to send or receive mail via their broadband links which have ISP's that differ to mine.
Chris

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    INITIATING CONNECTION May 16 16:28:27.927  -- host:mail.XXXXXXXX.com -- port:465 -- socket:0x0 -- thread:0x7ff5edab6270
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    WROTE May 16 16:28:28.477 [kCFStreamSocketSecurityLevelTLSv1SSLv3]  -- host:mail.nikiward.com -- port:465 -- socket:0x7ff5ee0dfbd0 -- thread:0x7ff5edab6270
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