Check the manufacturer's data sheet for the power supply to find out if the particular power supplies you want to connect in a series support a series connection. Do not connect the power supplies in a series if the manufacturer does not explicitly state that the power supply can be connected in series and does not provide a schematic for doing so.
Connect the negative lead of the first power supply to the positive lead of the second power supply.
Connect the positive lead of your voltmeter to the positive lead of the first power supply. Connect the negative lead of your voltmeter to the negative lead of the second power supply.
Turn on each of your power supplies and your voltmeter. Raise the voltage on the first power supply to 5 volts and the second power supply to 2 Volts. Read the voltage on your voltmeter display. Verify that it displays the sum of the voltage of the two power supplies, 7 Volts (5 plus 2 is 7). Check that your circuit is wired correctly if the voltage is not close to 7 Volts.