Aside from the pointwise characterization (i.e. the Sobolev–Slobodeckij spaces) mentioned in the comment. I believe the best motivation whose norm requires the complicated Littlewood-Paley decomposition is the theory of paraproduct.
Think about the Leibniz's rule on Sobolev spaces
$$\|fg\|_{W^{k,r}}\le\|f\|_{W^{k,p}}\|g\|_{L^q}+\|f\|_{L^p}\|g\|_{W^{k,q}},\quad\frac1p+\frac1q=\frac1r.$$
In order to make it more useful in PDEs we want to consider the concrete decomposition $fg=T_1(f,g)+T_2(f,g)$ such that $T_1:W^{k,p}\times L^q\to L^r$ and $T_2:L^p\times W^{k,q}\to L^r$ are bounded bilinear operators.
Roughly speaking $D^k T_1(f,g)\approx T_1(D^kf,g)$, and $T_1$ captures the "high frequency" of $f$. Similarly $D^k T_2(f,g)\approx T_2(f,D^kg)$.
To capture this idea one may want to use the Littlewood-Paley decomposition $f=\sum_jf$ and $g=\sum_kg_k$ (where $j,k\in\mathbb Z$ or $j,k\ge0$ depending on the context). In this decomposition $T_i(f,g)=\sum_{(j,k)\in\Lambda_i}f_jg_k$ where $\Lambda_1$ and $\Lambda_2$ are partition of the index space for $(j,k)$.
In general this also work for Sobolev spaces, which are special case of Triebel-Lizorkin spaces. But for the paraproduct decomposition along with their estimates, the Besov spaces should the best starting point.
I would recommend the book Fourier Analysis and Nonlinear Partial Differential Equations by Bahouri, Chemin and Danchin.