$\mathcal{E}$ is actually a ring isomorphism between suitably chosen rings.
Confusingly, this is actually not true.
This is because practically all known FHE schemes have each ciphertext have a "noise level" associated with it.
For example, let $\mathcal{C}$ be some (ring) of possible ciphertexts.
Let $\mathcal{C}^{\epsilon}\subseteq\mathcal{C}$ be a subset of this ring for ciphertexts of "noise level" $\epsilon$.
Then, one roughly gets that
$$\mathsf{Add}: \mathcal{C}^{\epsilon_0}\times \mathcal{C}^{\epsilon_1}\to \mathcal{C}^{\epsilon_0 + \epsilon_1}$$
$$\mathsf{Mul}: \mathcal{C}^{\epsilon_0}\times \mathcal{C}^{\epsilon_1}\to \mathcal{C}^{f(\epsilon_0,\epsilon_1)}$$
Here, $f$ depends on the particular FHE scheme under consideration.
Anyway, this "noise level" is important as decryption is only correct if the noise level is "small" (which is determined by the system parameters of the FHE scheme).
Consequentially, the following two situations are not equivalent
- doing some plaintext computation, and
- doing the same computation homomorphically, then decrypting.
They may be equivalent (i.e. the FHE may be correct) if the noise level is low enough.
But one can always specify computations (in terms of solely $\mathsf{Add}$, $\mathsf{Mul}$, or even only a single one of these algorithms) for which the noise level gets too large, and decryption would be incorrect.
Daniele Micciancio has discussed this nuance some in this talk, where he distinguishes between "Fully Homomorphic Encryption" and "Fully Composable Homomorphic Encryption", but I don't believe there is a corresponding paper (I haven't watched the talk in a while though).