Hi, it depends the context:
about understanding or well known, they are synonyms. You can use either, for example:
"entiendo lo que me dices" or "comprendo lo que me dices"
entender= well communication between 2 persons.- "nos hemos entendido perfectamente" or " nos hemso comprendido perfectamente"
on another context you can't use like synonyms,
comprender= to hold many elements or contains.- "la ciuddad esta comprendida por muchas calles, casas y edificios"
there are another cases, but in general this are the most important, only when your talk about understanding or knowledge can used like synonyms.