The answer is no.
Yes, if you only care about the amplitude of a repeating waveform, you can sample long enough and wait for the max.
However, you will need the signal to hold while each sampling is taking place - the adc module's datasheet for the acquisition time spec. Most onboard adcs are 1-2MSPS - NXP just announced a chip with extremely fast adc.
So what you want is really not doable on an avr, without outboard help - you can, for example, build a sample/hold circuitry. Though for a 4Mhz signal, it is not a sample task.