Discrepancy between measured and calculated value for capacitive divider
Assuming:

identical capacitor values
all capacitor initially discharged
leakage resistance much higher than 1 M \$\Omega\$

yes, after the transient (connection of the 5V DC source) and without the multimeter, the voltage should reach the expected value.
But, as soon as you connect the multimeter, it discharges that lower capacitor (5 times RC = 50 ms, assuming 10 M\$\Omega\$ input resistance).