The basic difference between postpositions (or prepositions) and cases is that cases take the scope of a single word, while adpositions can optionally take the scope of multiple words.
Both cases and adpositions serve to identify grammatical and locational roles in a sentence. When people think of case-marking, what they are usually thinking of something like Latin or Russian, so that the difference between Brutus Caesarem interfecit ‘Brutus killed Caesar’ and Brutum Caesar interfecit ‘Caesar killed Brutus’ is signaled not by word-order, but by an affix on the end of the word. In some languages, prepositions do the same thing. In Spanish, for example, the preposition a ‘to’ sometimes marks direct objects that are animate: yo veo a su gato ‘I see your cat’, where the direct object is signaled by a. This illustrates an important point: the difference between a case and an adposition is not about whether it’s an affix, but its distribution in syntax.
However, this fact is not always obvious, because in many languages postpositions often become cliticized (usually at the end) of the nouns they modify. So for example, the Georgian language has seven case suffixes that are always fused to the end of the noun, but it also has clitic postpositions:

So what really is the difference between these forms? How can we tell if the words on the left have cases, while those on the right have (mostly) postpositions?
There are a few clues. First, some of the postpositions also require a case form immediately before. This is possible in languages that allow case-stacking (Old Georgian and even modern Georgian sometimes is one), but it’s rare. More likely, one of those affixes is a case, and the other a postposition. But the real reason we know those on the right employ postpositions is that if you want to build a coordinate noun phrase, there is only one obligatory instance of the postposition:
sopel-sa da kalak=ši [village-DAT and city=in] ‘in the village and the city’
sopel-
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