The most important step for folks that wish to break free for Google: start using a custom domain name as soon as possible. Because the hard part is not moving from one email service provider to another, but getting your new email address in everybody's address books and changing all your site logins. And if you love your Gmail interface and all the goodies that come with it, thats fine. Get a 1 user Google Apps acco…
Or if you can't pay the 5$/month, you can get a free Zoho mail account with custom domain and connect Gmail to it.
Although, to be perfectly honest, I don't use any other product offered by Zoho.