In basic terms, the magnitude is not the only component of a vector like acceleration: its direction is, too. When the direction of a moving object changes -- even if it is moving at constant speed -- it is accelerating. In other words, the change in direction of a vector also contributes to changing its magnitude. This is better understood if you look at motion in, say, polar or spherical coordinates, where the centripetal term naturally pops out when you derive the general expression for acceleration.
Here is another way to understand this. In the diagram below, consider a particle moving with velocity $\mathbf{b}$ at time $t$ and subsequently with velocity $\mathbf{a}$ at time $t + \Delta t$. The magnitude of the two velocities are equal (i.e. the vectors are of equal length: $\mathbf{||a|| = ||b||}$.) The vector $\mathbf{\Delta v = a-b}$ denotes the change in velocity in time $\Delta t$. Clearly, $\mathbf{\Delta v}$ is also a vector in its own right, with a magnitude and a direction.
