I don't think if you have to be a magical girl fan to enjoy Madoka. I am not, unless you count Nanoha (a show that has much more fanservice than Madoka, not to mention all the mecha references), and still liked it a lot.

The main reason I didn't recommend Spice and Wolf is because of all the naked Horo at the beginning. If someone is rolling eyes at anime fanservice it won't help to change his mind, even if it pretty much never happens later.

Also, I forgot to mention Twelve Kingdoms. It starts like a cliche "high school girl gets spirited away to another world" anime, but it quickly turns into a socio-political tale about the responsibilities of a ruler and his relations with his vassals.

If movies and OVAs are okay, Macross: Do You Remember Love? is a very fun spectacle. It's not very deep and it stomps all over established Macross canon, but it's filled with high-quality eighties animation, is paced very well and is a good introduction to Macross.

Or you could watch Jin-Roh, which is a very somber anime movie without any fanservice or humour.