The first formula looks a bit better if you write it as KE=-PE=q.ΔV It describes what happens to a particle which moves to a new position where the difference in potential between these two positions is ΔV. KE=-PE comes from conservation of energy - another way to write it is KE+PE=0. Since the particle did not exchange any energy with other objects, it's total energy stays the same, only PE turns to KE or vise versa, depending on the sign of the change in potential.
The second formula tells you what the energy is to charge a capacitor to charge Q. Let's consider what this energy is. When you start, the capacitor is fully discharged. That is, the potential between the two plates is 0. To add a charge to it at that point requires 0 work. As you start increasing the charge on its plates, you also increase the potential between them and that starts to require more and more work to add the next discrete amount of charge. There are different ways to calculate what the sum of all these separate amounts of energy is but it all leads to a total of QV/2.
Just a quick hint about one way: the first charge needs 0 work. At that point the potential between the two plates is q/C, so the second one needs q*q/C amount of work. The third one has a potential of 2q/C and needs 2q*q/C of work and so on... the last one has a charge of(Q-q)/C and needs (Q-q)*q/C of work. When you do the sum of q/C(q+2q+3q+...+(Q-q)) you'll get Q^2/(2C) or QV/2.