In practice, most people would probably interpret these two sentences the same way, and I've never heard that "canceled" suggests a greater probability than "were to cancel."
However, strictly speaking, the two sentences do not mean the same thing. "If they were to cancel" uses the subjunctive mood, used to characterize hypothetical or counterfactual conditions. It implies that the cancellation decision has not yet been made, although I think it can also cover scenarios in which the decision has been made but you don't know the outcome yet, or in which you don't know whether the decision has been made yet or not.
"If they canceled" is not subjunctive, it is past tense indicative: it says that the decision to cancel or not cancel has already taken place, but the use of "if" says that you don't yet know the results of that decision. If that is indeed the case, I would suggest using "I will" (future tense) rather than "I would" (present subjunctive): you will learn the outcome of the decision in the future, and when you do, you will be devastated if the decision is to cancel.
So here are three possible sentences you could use, depending on the timing of the decision:
"If they canceled the deal, I will be devastated." (the decision has already taken place, but you don't know the outcome yet)
"If they cancel the deal, I will be devastated." (the decision will take place in the future)
"If they were to cancel the deal, I would be devastated." (works with past or future, or if you don't know whether the decision has happened or not)