Nice skirt! It reminds me of Diana's bubble skirt, just less voluminous.
I'm having a hard time seeing the detail in the pic with the black skirt, so I'll comment on the gray one. I really like the denim jacket with the skirt--it helps offset some of the lack of structure that you pointed out. As far as other ways to remedy the lack of structure, all I can think of is maybe wearing a tighter-fitting top instead of a looser-fitting T-shirt. (This is probably why I don't wear much unstructured clothing--I don't know what to do with it. :^))
My personal feeling is that the oxfords are a little heavy for this outfit. I don't quite know what to suggest instead. I think maybe you need something with a lower vamp. Maybe a flat, like in pic 1? Hopefully someone else will have some good input!
I know what you mean about wanting to break stuff out right away. I bought two faux leather skater skirts a week ago, and they are languishing in my closet. I want to wear them! But even with tights it is still too cold. But I think it is supposed to get up to the fifties this coming week, at which point I will break them out!