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Hmm. I'd say if you can manage it at all, try to get to
The Colour of Magic first.
These are probably the only two books within the Discworld universe where it's really, really helpful to have read the first one before proceeding to the next -- not only because
The Light Fantastic is a direct sequel to
The Colour of Magic, so the key characters are introduced (and of course are carrying quite a bit of a joint history by the time you get to
The Light Fantastic); book 1 also quite literally ends with a cliffhanger, which is resolved in book 2. I'm not sure how much sense the beginning of book 2 is going to make if you haven't read the end of book 1 first.
As Discworld books go, though, these are clearly the exception. After these, you can read any book in any order you please without bothering to get to the other ones from the same subseries first. Pratchett obviously learned from these two initial books and henceforth proceeded to incorporate whatever backstory you might need to know in the text of every new book he was writing. And that approach works very well!