Let's consider the state
$$|\psi\rangle=\alpha|0\rangle+\beta|1\rangle.$$
As you said, the magnitudes $|\alpha|^2$ and $|\beta|^2$ give you the relative probabilities of finding the state in $|0\rangle$ and $|1\rangle$ if you make a measurement in the $\{|0\rangle,|1\rangle\}$ basis.
There is more to it than the magnitudes however, because quantum mechanics is based on the idea of waves, and waves have both a magnitude and a phase. Imagine two sine waves of equal amplitude, what happens when you interfere them with each other? The answer depends on if they are in-phase (they sum to something with double the amplitude), out-of-phase (the result has zero amplitude), or something in between (somewhere between zero and double amplitude).
Similarly, when you see $\alpha|0\rangle$, imagine $\alpha$ as a ray in the 2D complex plane. This ray has magnitude $|\alpha|$, but it also has a phase. If we interfere our qubit $|\psi\rangle$ with another $|\phi\rangle=\alpha'|0\rangle+\beta'|1\rangle$, the result will be
$$\frac{1}{\sqrt{2}}\left(|\psi\rangle+|\phi\rangle\right)=\frac{\alpha+\alpha'}{\sqrt{2}}|0\rangle+\frac{\beta+\beta'}{\sqrt{2}}|1\rangle.$$
The coefficient of $|0\rangle$ is found by adding together the two rays $\alpha$,$\alpha'$, and similarly for $|1\rangle$ and $\beta$,$\beta'$. Even if $|\alpha|=|\alpha'|$, $|\beta|=|\beta'|$, the result will be very different depending on the phases.