The older you are, the less apt to want to bother you are: you want it to just work, and you don't have time to customize every little thing.
I think functionality overrides appearance, at least until competition steps in. Reddit and YC are examples of spartan design but great loyalty among readers young and old. It's the idea and the execution first followed by the quality of design.
We see it all the time: small company comes up with cool product but not-so-cool packaging/marketing. Once they become successful, they hire people who make their packaging/marketing as good as the product.
I guess I fall on the side of "Product First, Marketing Second." It could be that a great website design is more about marketing than product but I don't know.
Fantastic design is product first and marketing second. Marketing is about convincing you that you need something via a channel that is not the product itself.
The iPod is fantastic design. Myspace is absolutely hideous design.