Night Watch was amazing. Moral, moving, exciting. It could stand on it's own as literature without any of the other books.
Apart from his pun-a-thon books, most of his Discworld novels have some sort of moral underpinning. Small Gods on being religious versus being good is an obvious one, Feet of Clay being about slavery and what defines a person is another. But if you take a step back and look at most of his books, you'll find a moral lesson intentionally put in there.
Night Watch is amazing and moving.
Other Discworld stories that surprised me include Lords and Ladies and Thud!, in which Pratchett manages to write genuine horror stories.
So with the caveat that you need to understand those first two books aren't representative of what the series becomes, you could definitely start at the beginning. Just know that across so many books, there's bound to be some unevenness. Some books are just plain fun, others have deeper messages, some are, frankly, just not as good. Early highlights like Guards Guards, Pyramids, Small Gods, Wyrd Sisters are the ones where you'll discover the real breadth of what he does. Later books can be less consistently original, but when you get to books like The Truth, Night Watch and Monstrous Regiment, there are some real gems.
But don't let yourself not read any of them. That would be a real shame.