the first one, The Colour of Magic, is very good and might be a good one to start with. I personally like the ones about the witch Granny Weatherwax very much, the first of those is Equal Rites, which is another good one. guards! guards! Is the first of a number about the Night Watch, and is quite a good one. my personal favourites, and their main characters, are;
Reaper Man (Death and the Wizards)
witches Abroad ( Granny Weatherwax and Co)
the Last Continent (the wizards, and their housekeeper)
the Fifth Elephant (the Night Watch)
going Postal (a dashing conman)
unseen Academicals (the Wizards and their servants)
the Discworld has changed somewhat over time, in recent novels it has become less magical, and there tend to be fewer laughs and more discussion of social issues.