Why hello! I'm fairly new to statistics, which is why I'm somewhat confused as to how I can approach this problem in a scientific way.
The problem: Experiments are conducted to find the probabilities for several possible outcomes; let's say they are $X_1$ to $X_4$. There is no other outcome, so the "combined" probabilities must amount to $P = 1$ ($100\%$). It is, however, unknown how exactly this grand total is divided... It might be an equal $25\%$ or a random percentage between $0.01$ and $0.96$ for each.
The goal is to ultimately find out with a confidence level ($1\%, 3\%, 5\%$... doesn't matter) how the probabilities may be distributed among $X_1$ to $X_4$.
The hypothesis: It is thought that $X_1$ to $X_4$ have an equal probability of $25\%$ each. This is most likely wrong, but the hypothesis remains to be refuted by means of "proving" a different probability for each by observing a sufficiently large sample (the experiment mentioned above, which can be repeated indefinitely if need be).
Where I require your aid: Well... I have read up on everything I thought relevant to the problem, but I remain uncertain how to "formalize" everything. The calculations should be the lesser problem afterwards. When exactly will the observation sample size be large enough for a given confidence level? What kind of "mean" can I calculate from the observation if the individual events are different results and not simple numbers?
Say, $X_1$ -> "The computer catches fire" and $X_2$ -> "You win tomorrow's lottery" (random examples). They're not related to each other (such as $X_1 \rightarrow 1/\text{Heads}$, $X2 \rightarrow 0/\text{Tails}$), so I fail to see how I can apply the formulae available for mean, deviation, error and all the other possible statistical quantities I read about.
A couple preliminary clarifications/remarks on your problem:
From your wording, it appears that these probabilities are not only exhaustive but also mutually exclusive, so that one, and only one, outcome can occur in each experimental trial, correct?
What kind of confidence level do you want? I assume you want a set of family-wise confidence intervals, so that there is a, say, 95% confidence that all of the intervals cover the true probability of each occurrence.
I will assume the above in my answer.
When you are testing multiple outcomes that are related in some way (here, they are exhaustive so they add to 1) then you want to use the categorical distribution, which is related to the multinomial distribution not the normal approximation or the t-distribution for single-outcome statistics, as you have indicated. You are trying to force-fit a multi-dimensional problem into a one-dimensional testing scheme. The multinomial will give you the needed flexibility. As a basic primer on categorical data, see this.
To do a hypothesis test of equality of probabilities, you can use the Chi-square goodness of fit test, although it relies on a multivariate normal approximation to the set of estimated probabilities you get from the experiments. To get confidence intervals, see this.
I think the links and above explanations will get you largely where you want to go.