There are some circumstances where one cannot be substituted for the other. For example, in the sentence "there are even more people here than I expected" you cannot substitute "all the more". In general "all the more" cannot be followed by "than". However, in the sentence, "If you don't want any pudding that means even more/all the more for us" or in a sentence like, "She is keen on horses, but he is even more so/all the more so" the two phrases can be used interchangeably.