I am supposed to prove that
Let $X \ge 0$ be a random variable defined on $(\Omega, \mathcal{A}, > P)$ and $\mathbb{E}[X] = 1$. Define $Q: \mathcal{A} \to \mathbb{R}$ by $Q(A) = \mathbb{E}[X1_{A_n}]$. Show that Q is a probability measure on $(\Omega, \mathcal{A})$
Of course $Q(\Omega) = 1$. Now let $A_n \in \mathcal{A}$ pairwise disjoint events. Then
$$Q\left(\bigcup A_n\right) = \mathbb{E}\left[X1_{\bigcup A_n}\right] = \mathbb{E}\left[\sum X1_{A_n}\right].$$
Now can I say that $\mathbb{E}[\sum X1_{A_n}] = \sum \mathbb{E}[X1_{A_n}] = \sum Q(A_n)$, completing the proof?
I know that expectation is a linear operator, but how does it behave with countable sum?
You can pass to countable sums applying theorems like Monotone Convergence or Dominated Convergence. In your case, the monotone convergence theorems does the job, once the functions defined by
$$f_n = \sum_{i=1}^n X1_{A_i}$$
converge to
$$f = \sum_{i=1}^{\infty} X1_{A_i}$$
monotonically, right?
Then you have
$$\mathbb{E}[f] = \lim_n \mathbb{E}[f_n] = \lim_n \sum_{i=1}^n \mathbb{E}[X1_{A_i}] = \sum_{i=1}^{\infty} \mathbb{E}[X1_{A_i}]$$