Oh, I'm definitely an advocate of the publication chronology (
this list includes non-Discworld, including the 'prototype' that is Strata, but even just sticking to
this list would work) and it was the
only way for me to read them, as one eagerly awaited most of their publications after finding the first few in the library to prime me up. (Pratchett did for humorous but thoughtful situations what Piers Anthony basically tried to do with puns alone in the Xanth series.)
The actions of Small Gods (in the century before most of the other books' events) also introduce The Sweeper far in advance(!) of Thief Of Time, with The Truth setting up a couple of characters seen later in the Watch and Lipwig books (slightly more than cameos). There's very few truly stand-alones. The ones that appeared tended to spawn a continuation later on. The Amazing Maurice spun off a single-location scene 20 books earlier, in a newish part of the Disc not far from the areas dealt with 4 and 5 books earlier, but doesn't carry forward. Pyramids takes a pre-written AM guild experience over to a location barely mentioned in later works, though arguably it links into Small Gods, like Moving Pictures leads into various "Revolutionary Developments" successors.
It is
simpler to read them in published order, but I can imagine someone who really didn't get on with an entire arc finding being forced to endure that arc a discouragement in attempting to follow the 41 basic books. Being aware of which arcs there are and which books are in them could save that trouble.
But caveat lector. It's a body of work that
can be quickly addictive, or could just do with letting mature in the mind by revisiting some of them, from in amongst the whole series, and then appreciating the relative significance of the others.
(And you also have three made-for-TV movies/series, semi-direct from the books, which might be best watched only after reading the source material, plus two animations likewise. I
highly recommend the Soul Music one, for the songs progressing through genres, even if it butchers some of the plot along the way. But that's getting towards "advanced fandom" and getting away from reading. If I went on in that thread I might end up mentioning Discworld Noir (the third PC game, all new plot) or the
MUD!)