This is documented in my Icedove / Thunderbird guide.
### Signing by default.
Open Edit --> Account Settings --> OpenPGP security and select "Enable OpenPG support (Enigmail) with this user information". Then select "Use specific OpenPGP key" and press the "select key" button. Now just select your private key.
After you have selected the key, I recommend you to select the first and the second boxes, which are about signing.
Remember to do this for multiple identities. Select the account and then click the "manage identities" button.
To send PGP/MIME by default, open Edit --> Account Settings --> OpenPGP security and check "Use always PGP/MIME".
Remember to check to do this for your all identities in case you have more than one of them. Edit --> Account Settings --> "Manage Identities..." button and after selecting identity, you can find OpenPGP security tab.
# OpenPGP headers.
To enable sending OpenPGP headers, return to OpenPGP settings (mentioned above) and click "advanced".
Select the both checkboxes and write URL where your key is located. If you don't have homepage, you can link to webui of your preferred keyserver.
<arel="license"href="http://creativecommons.org/licenses/by-nc-sa/3.0/"><imgalt="Creative Commons License"style="border-width:0"src="http://i.creativecommons.org/l/by-nc-sa/3.0/88x31.png"/></a><br/><spanxmlns:dct="http://purl.org/dc/terms/"property="dct:title">Enigmail guide</span> is licensed under a <arel="license"href="http://creativecommons.org/licenses/by-nc-sa/3.0/">Creative Commons Attribution-NonCommercial-ShareAlike 3.0 Unported License</a>.<br/>Based on a work at <axmlns:dct="http://purl.org/dc/terms/"href="http://mkaysi.github.com/articles/guides/GPG/Enigmail.html"rel="dct:source">mkaysi.github.com</a>.