I realize now that I had assumed implicitely in my last comment that your matrix is already skew-symmetric, which is not the case.
Now that I have spoken about my misconception, I have realized that yours come mainly from the fact that (taking again the case $n=3$) a matrix with two complex conjugate eigenvalues and (therefore) a real eigenvalue is rather "distant" from a rotation matrix, as I will attempt to show.
In fact, there is a classical decomposition of any matrix under the form :
$$A=QR$$
classically called... "$QR$ decomposition" where $Q$ is an orthogonal matrix ($Q^T=Q^{-1}$, a rotation matrix if the eigenvalues are a real number and 2 complex conjugate values ; a symmetry matrix otherwise) and $R$ upper triangular.
Please note the order : $R$ is applied first, then rotation $Q$.
In very special cases, $R$ is diagonal : $R=diag(r_1,r_2,r_3)$ in which case, applying $A$ is equivalent to first scaling the 3 axis with these $r_1,r_2,r_3$ then applying the rotation. And in even more special cases $r_1=r_2=r_3=\rho$ which is the case I had too hastily privilegized.
But in general, upper triangular matrix $R$ induces an initial "scrambling" of the axes which makes things rather impossible to trace back, in particular regarding rotations.
Remark : in a different direction, the "closest orthogonal matrix" to a given matrix is given by the SVD decomposition ; see for example this question and its answer for a distance associated with the so-called Frobenius norm (see example below).
Let us take the example of
$$A = \pmatrix{ 0& 0&1\\
1&0&1\\
0&1& 0}$$
with real eigenvalue $1$ associated with $V=(1,-1,1)^T$.
Its QR factorization is
$$A=\underbrace{\pmatrix{ 0& 0&1\\
-1&0&0\\
0&-1& 0}}_{\text{rotation matrix} \ Q} \underbrace{\pmatrix{ -1& 0&-1\\
0&-1&0\\
0&0& 1}}_{\text{triangular matrix} \ R}\tag{1}$$
The characteristic polynomial of $P$ and $Q$,
$$\chi_A(x)=x^3-x^2-x-1, \ \ \chi_Q(x)=x^3-1$$
are different : their complex eigenvalues aren't the same therefore the angle of rotation will not be the same. But $A$ and $Q$ share the same real eigenvalue $1$ with the same associated eigenspace $\mathbb{R}V$ (for the eigenspace, i.e., for the axis of rotation, it needn't be the same one in general).
Besides, the closest orthogonal matrix to $A$ in the sense of Frobenius norm (as said above) isn't $Q$ as defined in (1) but
$$Q'=\pmatrix{-a&0&2a\\2a&0&a\\0&1&0} \text{where} \ a:=\frac15 \sqrt{5}$$
with characteristic polynomial :
$$\chi_{Q'}(x)=x^3+ax^2-ax-1=(x-1)(x^2+(1+a)x+1).$$
Still the same real eigenvalue $1$, but with a different associated eigenspace directed by $(1,\Phi,\Phi)^T$ where $\Phi=\frac12(1+\sqrt{5})$ (golden ratio).