Having never had a sibling, and having only one child myself, any opinions here are pure speculation. Chiyo-chan is obviously a good candidate, but I think I might prefer Haruka from Noein. She seems like such a good-natured, intelligent, and reliable girl.
I just realized both these girls are only-children themselves.
Edit: You know, just about any anime girl or woman could be my "little" sister. Of
these, I'd pick Nakajima Youko from Junni Kokki.