I saw in the announcement that live.com email addresses are finally available, but couldn't figure out where you'd go to get one. Fortunately, LiveSide has the scoop:

Microsoft just enabled the @live.xx signup! Go grab yours now! http://get.live.com/getlive/overview for the local domains (eg @live.co.uk) or use the following link for @live.com - @live.com signup.

Regarding the transition from @hotmail.com to @live.com, a pretty straightforward process is given on the new Windows Live site at http://www.windowslive.com/freshstart.

Thanks Troy!