4kV typically means the insulation is rated for 4kV RMS AC. Peak-to-peak is 2 * sqrt(2) * Vrms (for sinusoidal waveforms).
Voltages are typically given as phase-to-phase, assuming the system is solidly grounded. For system that are impedance grounded (where ground offsets occur only during faults), 133% rated insulation is usually specified. Many engineers also specify 133% for solidly grounded systems for a little safety factor. For ungrounded system, use 173%.