We have just made the move  from 32-bit to 64-bit, with no major issues. Are you
going to connect the databases  to your current environment, or moving  to a new
environment?

I was hoping to use current environment which consists of 1 web front
end and 1 Index server.

Start here: technet.microsoft.com/en-us/library/cc263447.aspx There is a
digital book too at the bottom of the page that addresses upgrade paths. There
may be more information there.

Also, I share this site as a good source for those wanting to understand all the
different db(s) that make up your farm. SEE here:
grounding.co.za/.../sql-databases-used-in-share\
point.aspx

Good luck. Be sure to write back what you end up doing and the results and
lessons learned.

Has anyone had any experience migrating their content database from SQL 2005
to SQL 2008 on another box? If so are there any resources out there that you
could point me to?

I've done it. There's not much to it. You can restore SQL 2005 database
backups to SQL 2008 without any other work. SQL is good about upgrading
databases when you attach it. Read through this, too,
stsadm.blogspot.com/.../...databases-easy-way.html It
doesn't call out SQL versions, but it doesn't have to. There's no extra
prep.

we did a couple of practice runs to make sure we could make the move  with no
issues, and like you said, there is not much to it.