Do you think they can handle Small Gods? It's technically chronologically first (unless you count parts of Eric and/or The Last Continent), is a self-contained standalone story which later has resonance on others, and manages to introduce important stuff like Death and the History Monks and L-Space without requiring any foreknowledge, and happens to be one of the very best books in the series, IMHO.
ETA: I should note that I did in fact first read this myself when I was about 12.
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