Conclusion of a discussion I had with ento about the restriction of usage of もっと:
Consider:
A: XとY、どちらのほうが安いですか
B: Xのほうが、Yよりもっと安いです。
もっと sounds strange in this case because it implies that Y actually is "安い" to a degree. B is comparing the cheapness of the two, when A is just comparing their prices.
Comparing the cheapness of the two is different from comparing their prices.
Even though B's response satisfies what A asks, but at the same time, B slipped in a subjective judgment that X and Y are cheap.
That is to say that by using もっと, it reveals that B has a presupposition that both items are cheap, which is not necessarily the case, nor has been implied by A. So the introduction of this irrelevant presupposition makes the the use of もっと strange.
So for もっと to be used, there should be a precedent for which the "whatever-ness" you wish to express has already been established, and you wish to express more of it.
To answer "Why or why not would the two be interchangeable?", I would say changing them would change the perception of circumstances that the sentence is in:
If the sentence is 危険性がもっと大きい。
, もっと
would create the perception that it is already 危険性が大きい
and you are expressing even more.
For それはもっと大きい夢である。
It creates the perception that the 夢
was already 大きい
.