Say I have $3x-2 = |x|$. Why can't I just do this:
$3x - 2 = -x$ and $3x - 2 = x$
and then get two values for $x$: $1$ and $0.5$? I know the answer $0.5$ doesn't work if you plug this in. However, I don't understand why we can't solve the equation like this?

The solution method you followed has a graphical interpretation. If you graph the lines $y = 3x - 2$ and $y = x$, their intersection will give one of the values of $x$ your method finds (specifically, where $3x - 2 = x$). The intersection of the lines $y = 3x - 2$ and $y = -x$ gives your other value of $x$:
That is, $x = 1$ at the intersection with the line $y =x$, and $x = 1/2$ at the intersection with the line $y=-x$. There's just one problem: the graph of the function $y = |x|$ includes only the parts of the lines $y=x$ and $y=-x$ colored solid black in the diagram below:
So we see that only one of the two intersections is actually on the graph of $y = |x|$, and this is the only valid solution to the equation $3x-2 = |x|.$
One way to look at this is the intersection with $y = x$ is valid only if it occurs for $x \ge 0$, while the intersection with $y = -x$ is valid only if it occurs for $x \le 0$. Another way to look at it is that the intersection is valid only if $y \ge 0$.
If you had been trying to solve a different equation, however, you might have gotten two solutions. For example, consider the equation $\dfrac{x+2}{3} = |x|$, solved graphically below. In this case both of the intersections with the lines $y = x$ and $y = -x$ occur on the "correct" portions of those lines.