There are a few methods here:
First, is the continuation of yours: As you've observed, $F(x_1, y_1) = F(x_2, y_2)$ implies
\begin{align}
2 x_1 + y_1 &= 2 x_2 + y_2 \\
x_1 + 4 y_1 &= x_2 + 4 y_2 .
\end{align}
Respective subtracting twice each side of the second equation from each side of the first give
$$- 3 y_1 = - 3 y_2,$$
and multiplying both sides by $-\frac{1}{3}$ gives
$$y_1 = y_2$$
as desired. An analogous pair of operations gives $y_1 = y_2$.
Alternatively, we can simply look for an inverse: That is solve $(u, v) = F(x, y) = (2 x + y, x + 4y)$ for $x, y$ in terms of $(u, v)$. If we can do so, $F$ is invertible, with inverse $F^{-1}$ given by this expression.
Finally, since $F$ is linear, we may write it in matrix form:
$$F\left(\begin{pmatrix}x\\y\end{pmatrix}\right) = \begin{pmatrix}2 & 1\\1 & 4\end{pmatrix}\begin{pmatrix}x\\y\end{pmatrix}.$$
If the $2 \times 2$ matrix is invertible, then we can solve for $F(x, y)$ in terms of $(x, y)$, which shows that $F$ is invertible:
$$\begin{pmatrix}x\\y\end{pmatrix} = \begin{pmatrix}2 & 1\\1 & 4\end{pmatrix}^{-1}F\left(\begin{pmatrix}x\\y\end{pmatrix}\right).$$
To show that this matrix is invertible we need not compute its inverse directly---a matrix is invertible iff its determinant is nonzero, which is the case for this matrix:
$$\det \begin{pmatrix}2 & 1\\1 & 4\end{pmatrix} = (2)(4) - (1)(1) = 7 \neq 0.$$