My Developer Edition org doesn't have Sites as an option under Setup | Develop.

Is this something that I can get enabled with a case to support, or am I better off starting a new developer org?

My org is cira 2007.

I found the post Enable SITES to Developer Edition Org, which makes it look like I'll need to get a new Org:

Thank you for contacting Salesforce technical support! My name is Ana and I have recently taken ownership of your case.

I understand that you are requesting to have sites enabled for your developer edition. Unfortunately, your developer account was created before sites existed as a Salesforce feature. I am afraid but we cannot enable sites for your developer account.

We really apologize, I understand that you wanted to utilize this org as much as possible, having a fair amount of "tutorial" work done on it. But I have exhausted all my resources to see if there is a work around, the only recommendation to have sites is to create a brand new Dev account with all the recent features included.