The property of being positive definite/semi-definite does not change if we switch from a matrix $A$ to a similar matrix $PAP^{-1}$ with an invertible matrix $P$. In particular, we can diagonalise $A$ using an orthogonal matrix $P$, i.e. $D=P^{-1}AP$ for some orthogonal matrix $P$ and diagonal matrix $D$. All the entries on the diagonal of $D$ are positive as $A$ is a positive-definite matrix.
Now, if $A$ is similar to $D$, then $A+A^{-1}-2I$ is similar to $D+D^{-1}-2I$ because:
$$P^{-1}(A+A^{-1}-2I)P=D+D^{-1}-2I$$
However, $D+D^{-1}-2I$ is also diagonal, and if the entries on the diagonal of $D$ are $d_i, i=1,\ldots,n$, then the entries on the diagonal of $D+D^{-1}-2I$ are $d_i+\frac{1}{d_i}-2=\frac{1}{d_i}(d_i-1)^2\ge 0$. Thus, the matrix $D+D^{-1}-2I$ is positive semi-definite, and so the matrix $A+A^{-1}-2I$ is positive semi-definite.
Therefore, the matrix $A+A^{-1}-2I$ is always positive semi-definite. It may not be positive definite, as the example $A=I$ shows.