 Solution

Fourier orthogonality isolates a coefficient. Multiplication by $\sin (mx)$ and integration over $[0,2\pi ]$ annihilates the constant, all cosine terms and all sine terms except the one with $n=m$, whose squared integral is $\pi$. Thus the corresponding coefficients on the two sides must agree for each positive integer $m$.

Multiplication by $\cos (mx)$ works in the same way, while integration against the constant mode extracts $a_0$. This is the uniqueness of the Fourier coefficients; it does not follow from comparing a few point values of the series.