then we always feed that value of resistor divider to an op amp
Not always.
What exactly does the op amp do in this case?
To answer your question, let's first have a look at the divide-and-measure network:
simulate this circuit – Schematic created using CircuitLab
When you connect the divider to the ADC input, the input impedance of the ADC (represented as Rin) will be a part of the divider. Depending on the MCU used, the value of Rin can be as high as hundreds of kiloohms, or even a few megaohms. You should always check the datasheets for that specific value/information.
In applications where the divider resistors (Ru and Rd) have to be very high due to strict consumption limitations, the input impedance of the ADC will simply "disturb" the divider and change the division ratio. For example, let's assume the input impedance of the ADC channel (Rin) is 500k, and the divider resistors, Ru and Rd, are 500k and 100k, respectively. The divider on its own is expected to have a division ratio of 100/(100+500) = 1/6. However, since the Rin is in parallel with Rd, makes the effective resistance 83k, and decreases the division ratio to 1/7. This will, of course, lead to false measurements.
Here, one may ask the possibility of removing Rd and using Rin on its own as the low-side resistor of the divider. Electrically, it's possible. However, Rin is not generally a fixed resistance i.e. it can vary with operational parameters such as clock frequency or sampling rate, or even chip to chip. So, Rin is a thing of which the effect should be compensated or kept as low as possible, for reliable operation.
To mitigate this, an op amp having very low input bias currents can be placed after the divider as a buffer (i.e. unity gain), and its output can be fed to the ADC because the op amp's output impedance is low enough not to interact with the input impedance of the ADC:
simulate this circuit
So,
Why we can't feed output of divider directly to ADC of micro controller?
We can, if the divider resistors can be kept low enough. Generally, a few tens of kiloohms for Ru and Rd doesn't bring any need of an op amp. For the same example above, if the divider resistors were 50k and 10k instead of 500k and 100k, the net division ratio would be 1/6.1 which is only 2% less than 1/6. Depending on the accuracy needs, op amp may further decrease the shift.