The collection of solutions you find by assuming separability is much richer than the collection of simple polynomial solutions you find by taking $u(x,t) = X(x) + T(t)$. In particular, by taking linear combinations of separable solutions, we can solve any given initial-boundary value problem (IBVP) for the heat equation.
I'll show how this works out in detail. The following material can be found in PDE textbooks such as Boyce and DiPrima.
For example, consider the following IBVP: Find a continuous function $u: [0,1] \times [0,\infty)$ such that $u$ satisfies the heat equation $u_t = u_{xx}$ on $\Omega = (0,1) \times (0,\infty)$ as well as the boundary conditions $u(0,t) = u(1,t) = 0$ (for all $t > 0$) and the initial condition $u(x,0) = f(x)$. Here $f:[0,1] \to \mathbb R$ is any given continuous, piecewise differentiable function that satisfies $f(0) = f(1) = 0$. (Other assumptions on $f$ are also possible, but the restrictions on $f$ are always very mild.)
First we find separable solutions to the heat equation which satisfy the given boundary conditions. If a separable function $u(x,t) = X(x) T(t)$ satisfies the heat equation on $\Omega$, then there must exist a constant $\lambda$ such that
$$
T'(t)/T(t) = X''(x)/X(x) = \lambda
$$
for all $(x,t) \in \Omega$. If $\lambda$ were positive, our boundary conditions could not be satisfied. If $\lambda = 0$ then $u(x,t) = 0$, a trivial solution. So we assume that $\lambda$ is negative.
It follows that $T(t) = T_0 e^{\lambda t}$ and $X(x) = a \cos(\sqrt{-\lambda} x) + b \sin(\sqrt{-\lambda} x)$
for some constants $T_0, a$, and $b$. Now plugging in the boundary conditions $u(0,t) = u(1,t) = 0$, we find that $a = 0$ and $b \sin(\sqrt{-\lambda}) = 0$.
Assuming that $b \neq 0$, it follows that $\sqrt{-\lambda} = n \pi$ for some positive integer $n$. So the separable solutions we have found are
$$
u_n(x,t) = c e^{- n^2 \pi^2 t} \sin(n \pi x) \quad \text{for } n = 1, 2, \ldots.
$$
Now we solve the IBVP given above by seeking a solution of the form
$$
u(x,t) = \sum_{n = 1}^\infty c_n e^{-n^2 \pi^2 t} \sin(n \pi x).
$$
This $u$ automatically satisfies $u_t = u_{xx}$ as well as $u(0,t) = u(1,t) = 0$ for all $t > 0$. The only issue is to make $u$ satisfy the initial condition
$$
u(x,0) = f(x).
$$
This initial condition can only be satisfied if there exist constants $c_n$ (for $n = 1, 2, \ldots$) such that
$$
f(x) = \sum_{n=1}^\infty c_n \sin(n \pi x).
$$
Now here is the amazing part: it turns out that any function $f$ satisfying the above conditions can be represented like this! That is a fact from Fourier analysis. Fourier made this claim, optimistically, but no one believed him at first. If I understand the history correctly, this is the thought process that led to the discovery of Fourier series --- a momentous moment in the history of math. Why math tends to work out so nicely is a deep mystery, a glimpse of perfection in the universe.
So by taking linear combinations of the separable functions we are able to solve our IBVP. This wouldn't have worked if we had tried to find a solution $u$ that is a linear combination of the simple polynomial solutions mentioned in the question. In particular, the step where we have to represent $f$ would have failed.