I have been a big fan of scarves since highschool. There are a lot of different ways you can use a scarf to make an outfit more interesting.
Back when I had long hair, I would tie a scarf around the top of my ponytail and braid it in with the hair, then use the loose ends to tie off the end of the braid, which looked pretty cool.
Or sometimes, I would tie it in a huge bow on the back of my head, like a little Victorian girl.
Now that my hair is short and spiky, I sometimes pull the front of it forward and tie a scarf around the crown of my head and let the ends hang loose down my back. It's kind of punky. It was inspired by some pictures I saw of Japanese girls who had similar haircuts, where it is all short, but the top and front is a little longer and made all spiky with gel. The way I wear the scarf is a little like Nicole Ritchie's ubiquitous hairbands, but it looks tougher because I have a more wild haircut and use gel to make it messy and spiky.
I also like scarves for belts.
I don't wear them around my neck, however. For me, it just doesn't feel or look natural. I think the look may be too demure and preppy for me.