Multiple identities per e-mail account
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You can tell Thunderbird to use more than one identity (personality) per mail account. This lets you select the desired From: address from a drop down list when composing a message, have the From: address default to whatever email address a message was sent to when replying, or use a different set of customized settings when sending a message. This is useful when you:
This doesn't require you to add another account or use a different SMTP server. You are merely enhancing an existing account.
How to add another identity:
When you write a new message, Thunderbird uses the default identity for the account you are working in. When you reply to a message, Thunderbird uses the identity that matches the address the message was originally sent to, if it can find a match in the account you are working in. Otherwise it uses the default identity. Set mailnews.reply_to_self_check_all_ident to true using the Config editor if you want it to check the identities for all accounts when replying.
You can select any multiple identity when replying, forwarding or composing a new message by selecting it in the From drop down list box. That identity (except for the From: address) defaults to the accounts settings but it can be modified to use different settings such as a different signature, draft folder, "sent" folder, SMTP server etc. using the Edit button in the Manage Identities window.
Thunderbird will let you select any accounts From: address in the From: drop down list. However, in most versions that identity is not actually used unless its either the current accounts identity, a multiple identity defined for the current account or you set mailnews.reply_to_self_check_all_ident to true.
Messages sent using mailing lists frequently don't specify what address the message was sent to in the To: or Cc: headers. It might be buried in one of the Received: headers, or in mailing list specific headers such Delivered-To: or Envelope-To: that Thunderbird has no knowledge of. In that case, Thunderbird doesn't know how to match the address the message was originally sent to and will typically select the default identity. If that happens you need to manually select the appropriate identity from the list box. If you use a separate folder for mail sent to each mailing list one workaround would be to use the Folder Account extension to specify what identity to use when a specific folder is selected.
The Gmail SMTP server will ignore whatever From: address you supply unless you add it in the Gmail web page at Setting -> Accounts -> "Add another email address". The AOL and AIM SMTP servers won't accept a email address that doesn't match the the screen name used to authenticate when sending.
Thunderbird 2 changed the behavior when replying to a sender, where the sender is one of your multiple identities. It used to reply to that identity, now it uses the default identity. According to this bug report its by design.
Folder specific settings
The Folder Account extension lets you select what account or identity will be used when composing, replying, or forwarding mail based on what folder is currently selected. It also lets you specify the default To: address when composing a message based on the currently selected folder. Right click on the folder and select properties in order to configure the account/identity and/or To: address.
You can still select a different identity from the From: drop down list box if you use this extension.
Recipient specific identities
The Flexible Identity add-on lets you configure what identity to use based on who you are sending a message. It supports both simple filters and regular expressions in its rules, and has a option to warn you whenever it applies a rule. This can be useful if you are worried about accidentally using a personal email address when replying to work related email (and vice versa).
If occasionally you want somebody to reply to a different email address you don't have to specify a different From: address. Just choose Reply-To: using the To: list box near the top left corner of the compose message window. Don't forget to also add a To: or Bcc: address.
S/MIME and Enigmail
The S/MIME certificate only applies to the accounts default identity. You need to copy the settings from the default identity to mail.identity.idN.encryption_cert_name , mail.identity.idN.encryptionpolicy, mail.identity.idN.sign_mail , and mail.identity.idN.signing_cert_name .