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Spammers will always spoof the from address so your best bet is to improve your anti-spam. There are a lot of ways of doing this and some are documented on that Wiki article. You could also look at implementing DKIM aswell.
Is there any setting in zimbra, so whenever zimbra user got mail from outside world, zimbra should check whether it is from valid domain or it is valid user of that domain
If you are not using a catch all account on your domain then if that recipient does not exist the email will be rejected. If you do have a catch all account then by the nature of its purpose it will still accept the email even if the recipient does not exist.