In this answer, Ben Grossmann said that $\operatorname{span}\{P:P \succ 0\} = \{A:A = A^T\} =: \mathcal S$. I am not sure, however, why this is true. Also, I guess $\operatorname{span}\{ P:P\succeq 0 \} = \operatorname{span}\{ P:P \succ 0 \}$?
I tried to use symmetric eigenvalue decomposition and also $P=B^{2} = CC^{T}$ but both did not work. So how can we write a symmetric matrix as a linear combination of positive (semidefinite) matrices?
Every linear combination of symmetric positive matrices is a symmetric matrix. Therefore the linear span of positive definite matrices is a subset of all symmetric matrices.
For the reverse inclusion, observe that for any symmetric matrix $A$, the sum $A+cI$ will be positive definite matrix when $c>0$ is sufficiently large. (In particular, $A+cI$ is guaranteed to be positive definite if $c>$ the spectral radius of $A$.) Hence $A=(A+cI)-cI$ is the linear combination of two positive definite matrices $A+cI$ and $cI$, i.e., $A$ lies inside the linear span of all positive definite matrices.