The way I understand it (I'm not too sure though) is that a POVM is a set of operators, each of which represents a possible result in your experiment. Unlike the operators for "observables", in which the eigenvalues are the physical values that may be found in the measurement (with units!), these operators have eigenvalues that are numbers between zero & one. The physical meaning of the eigenvalue is that if the measured system is in the associated eigenstate, then the result represented by this particular operator will occur with a probability given by the eigenvalue. More generally, if the system is in state ρ, then the result represented by operator E will occur with probability Tr(ρE).
This is quite different from a "standard" or ideal measurement, in which we know with certainty that if the system is in an eigenstate of the observable, we will definitely find the result given by the eigenvalue. That can be represented by a set of operators that have only 0 or 1 as eigenvalues- namely, projectors. Then the only sources of randomness in the result are the Born Rule probabilities when the state is in a superposition of eigenstates, and/or our lack of knowledge about the state, represented by ρ being mixed. The POVM formalism allows us to describe more realistic measurement scenarios, in which there usually are many other probabilistic factors at play as well.