Two questions:
I need some 500 miles more and was wondering if I could book a flight for my husband online and this way get the 500 miles for online booking instead of him? I'm not booking for myself.

I suppose the answer is No but you never know.
Secondly: I'll have a multileg business trip coming up soon. At the last location I'll meet my husband and we'll be flying home on the same plane. How can we be sure to sit together? So far our seat selections have been ignored several times due to families wanting to sit together, but normally our tickets are booked together, thus while we get moved away from a window seat we at least still sit together. This time our tickets will not be booked together.