Steve Earle sang back in 1994 about a crush on Condoleeza Rice. She was the Secretary of State for President George W. Bush and also, his national security adviser.
A national security adviser is an appointed position in US government. The White House position provides advice and briefings to the President on matters of… you guessed it: national security. Principally under Bush, this was about terrorism, but also Israel and Iraq. A controversy during Rice’s time in this position was the degree to which she oversaw or authorized torture (waterboarding) of Al Qaeda.
The Secretary of State position, also appointed by the President, would be like the President’s cabinet ministers – again, advisers in different areas, this one being foreign affairs. One difference is that a secretary position, unlike the national security adviser, must also be confirmed by the Senate.
The song’s narrator, asking “Condi” out for a date, may be suggesting that there is a different, warmer side to her not permitted to be revealed given her positions in the Bush administration.