Sean Wallbridge
Well, I helped solve this by accident, but mostly Zac came to this conclusion.
Problem:
You have a SharePoint list/form that you want to control the order of data entry into. No matter what way you order the columns in the list or view, it doesn’t show them the way you’d expect.
Answer:
The column ordering is based on the content type’s ordering, and then list settings ordering is applied after. I think the rules are that it applies the content type’s ordering first, and then orders any additional columns that you have added later.
To change the ordering of the content type, you need to first enable the management of content types on that list (Advanced settings), then select the content type (Issue, in my case), and re-order the columns there.
Zac wrote and discovered it first, so it would be rude not to point out the reference 🙂
http://www.sharepointu.com/forums/p/1494/4056.aspx