PCA gives you a decomposition of the covariance matrix of the form
$$
\Sigma = V \Lambda V^T
$$
where $\Lambda$ is diagonal with the eigenvalues in the diagonal.
Your portfolio variance is
$$
w^T \Sigma w = (V^T w )^T \Lambda (V^T w)
$$
On the other hand if you take your return matrix $R$ and define
$$
F = V^T R
$$
then the covariance matrix of these so called principle portfolios is $\Lambda$.
You find this here by Meucci.
In fact he writes $V^{-1} R$ for the return of principle portfolios
and defines the weights $w^* = V^{-1} w$ for the weight of the original portfolio on the principle portfolios.
He then defines $v_n = (w^*)^2 \lambda_n^2$ for the contribution of the n-th principle portfolio to the portfolio variance. If you relate this to the total volatility of the portfolio then you are done. Note that $V$ is orthogonal which means that $V^{-1} = V^T$.
I recommend to read the following white paper or this blog entry or this to get more details.