Publication order is probably fine - Color of Magic is definitely not as good as, say, Interesting Times (and that's without even leaving the books that have Twoflower in them!) but it's not bad by any stretch - and has the advantage of being absolutely the simplest approach.
If you want to get a decent idea of the books and only read, say half a dozen, the City Watch sequence (start with Guards, Guards, Men at Arms, Feet of Clay) is pretty great.