I've been having the exact same issue, and after a long night I believe I have it sorted out.
1) Make sure you have an SPF record set up for your domain.
2) Set up DKIM on your mail server and put your public key in your DNS (TXT record).
3) Make sure your html email is properly formatted ( I had to add the html opening and closing tags to mine, Devise did not do this by default).
4) The last piece of the puzzle was making sure I was sending both plaintext and html MIME parts in my emails. Just creating an additional plaintext 'text.erb' file for each of my mail views seemed to do the trick (Rails auto-magically picked it up and constructed multipart emails for me).
You can verify 1 and 2 are setup right by viewing the 'original' email within Gmail and making sure you see something like "spf=pass" and "dkim=pass" in the headers.
A friend informed me about a service called SendGrid (and I'm sure there are other service providers that do exactly the same thing) after I had spent nearly an entire night going from WTH is DKIM? -- to getting way more familiar with SMTP, DNS, and postfix than I ever wanted to be. But it works now, and I'm probably too cheap to pay for a third party service anyway :)