I have been asked recently for the required steps to configure Autodiscover when having Multiple SMTP namespaces, I have started writing few lines then upon checking my favorites I found a great bunch of blogs which explains the two possible solutions in great details, so here we go:
http://blogs.technet.com/b/jmayans/archive/2006/09/07/454716.aspx
http://www.more2know.nl/2010/05/18/exchange-autodiscover-and-multiple-domains/
background:
http://technet.microsoft.com/en-us/library/bb332063(EXCHG.80).aspx
http://support.microsoft.com/default.aspx?scid=kb;EN-US;940881
For folks also using Lync Enterprise Voice and Lync Phone Edition devices, it's important to note that only the multiple-name-in-SAN approach works any longer.
social.technet.microsoft.com/…/lync-phone-edition-cant-retrieve-autodiscoverxml
A recent CU for Lync Phone Edition has broken the other (SRV and redirect) approaches.