In the meantime, I came to know that the requirement is within IS 1644 - 1988, Code of Practice for Fire Safety of Buildings (General): Exit Requirements and Personal Hazard.
I have gone through it. There is nothing specifically mentioned about Electrical Sub-stations. However, I think with the following statements from IS 1644, we can conclude that it is required for substations as well:
"2.7.1 General Requirement - All buildings which are more than 15 m in height and all buildings used as educational (B), assembly (D1), institutional (F), industrial (G1), storage (H), and hazardous (J) occupancies and mixed occupancies with any of the aforesaid occupancies, having an area more than 500 m² on each floor should have a minimum of two staircases."
"2.7.13 Industrial (G) 2.7.13.1 Not less than two exits should be provided for every floor or section, including basements used for industrial purposes or uses incidental thereto."
If any of you have further inputs, please let me know.
Regards,