We start with
$$\int_0^{\pi/2} \dfrac{1}{2-\cos{x}} dx$$
Let's start as you suggest and see where it takes us, multiplying top and bottom by $2 + \cos x$.
$$ \int_0^{\pi/2} \frac{2 + \cos x}{4 - \cos^2 x} dx = \int_0^{\pi/2} \frac{2 + \cos x}{3 + \sin^2 x} dx.$$
The mathematics of wishful thinking suggests that we split this integral and handle the easy part first.
$$ \int_0^{\pi/2} \frac{\cos x}{3 + \sin^2 x} dx = \int_0^1 \frac{1}{3 + u^2} du$$
when we perform the substitution $u = \sin x$. This is now a classic inverse trigonometric integral, and will lead you to $\arctan$.
What did we leave behind? We left
$$ \int_0^{\pi/2} \frac{2}{3 + \sin^2 x} dx.$$
This looks a bit tricky. One way to proceed is to recognize $3 = 3\sin^2 x + 3 \cos^2 x$, so that we have
$$ \int_0^{\pi/2} \frac{2}{3 \cos^2 x + 4\sin^2 x} dx.$$
Now multiplying by $\sec^2(x)/\sec^2(x)$ gives
$$\int_0^{\pi/2} \frac{2 \sec^2 x}{3 \cot^2 x + 4} dx.$$
Now you can finish with the substition $u = 3\cot^2 x + 4$.
Is this what I'd recommend? It's hard to say. The substitution you mention is a well-known substitution. But it's important to recognize that with these problems, as long as you follow your nose and charge forward, you'll probably reach a resolution.