There is quite a lot of really nice stuff to dig through. The Discworld one offs are usually a good start. Small Gods does a nice little thing about religion while Soul Music and Moving Pictures do rock music and golden era Holywood respectively.
For an introduction to the universe itself Color of Magic and The Light Fantastic is a good start.
But basically it is all good and like with Douglas Adams the big plotline is most of the time secondary to what the small things say about humanity.