You would say "J'habite au Cap-Occidental en Afrique du Sud."
Why "a" was not used here instead of "au"
We say "au" as the name of this place is "Le Cap-Occidental". "Au" is the contraction of "à" + "le".
You can get more information here: Definite articles contract with à and de in French (French Contracted Articles)
Hope this helps!
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