First of all, Baire and Borel functions are the same here, since $\text{Spec}(a)$ is a compact subset of $\mathbb{C}$.
Iterated applications of monotone limits are enough to obtain all pointwise limits, whence all bounded Borel functions. Restricting to monotone convergence is not necessary - either iterated monotone convergence or iterated pointwise convergence will give you all bounded Borel functions. So the result is the same either way. (But it is easy to show that monotone limits exist for operators, so perhaps that’s why the author put it that way.)
$L^\infty(\text{Spec}(a)) \simeq W^\ast(a, 1)$ is true - under the assumption that your Hilbert space is separable, and that you can choose what measure to use on $\text{Spec}(a)$, as the correct measure to use may not be the Lebesgue measure - but it is not what the quote is claiming. Recall that $L^\infty(\text{Spec}(a))$ only makes sense when you have a measure on $\text{Spec}(a)$, and it identifies two functions if they are a.e. equal. Instead, the author simple claims there is a surjective $\ast$-homomirphism:
$$\mathcal{B}^\infty(\text{Spec}(a)) \to W^\ast(a, 1)$$
Where $\mathcal{B}^\infty(\text{Spec}(a))$ is the algebra of all bounded Borel functions on $\text{Spec}(a)$, where we do not have a measure specified, nor do we identify functions up to a.e. equivalence. This is indeed true, assuming the Hilbert space is separable (in that case you can actually choose a probability measure $\mu$ on $\text{Spec}(a)$ and the surjection is effectively identifying functions up to a.e. equivalence w.r.t. $\mu$). However, first remark: this may not be true if the Hilbert space is not separable. For example, the operator $a$ on the sequence space $\ell^2([0, 1])$ given by $ae_t = te_t$ for all $t \in [0, 1]$. $W^\ast(a, 1)$ consists of multiplication by all bounded functions on $[0, 1]$ along the diagonal, but the range of the map $\mathcal{B}^\infty(\text{Spec}(a)) \to W^\ast(a, 1)$ (known as the Borel functional calculus) only consists of multiplication by bounded Borel functions along the diagonal.
Second remark: even if the Hilbert space is separable, whence the map is surjective, it needs not be injective. For example, $a$ being multiplication by $t$ on $L^2([0, 1], m)$, where $m$ is the Lebesgue measure. Then for $f$ being the indicator function of a singleton (or any nonempty Lebesgue-null set, for that matter), $f(a) = 0$ despite $f \neq 0$. (In fact, one can show that, assuming the Hilbert space is separable, the Borel functional calculus map is injective iff $\text{Spec}(a)$ is countable and every point in the spectrum is an eigenvalue of $a$. In particular, even $\text{Spec}(a)$ being countable is not enough by itself. For example, if $a$ is a normal, compact, and injective operator on an infinite-dimensional Hilbert space, then $0 \in \text{Spec}(a)$. If $f$ is the indicator function of $\{0\}$, then $f \neq 0$ but $f(a) = 0$.)