I'd have to give the nod to Lyndon Baines Johnson, President form 1963 - 1969. While George W. Bush is certainly known for No Child Left Behind, I believe history is going to give LBJ much more credit for being an education President.
There were two laws that really set LBJ apart. First, the Elementary and Secondary Education Act of 1965 gave large amounts of federal money to public schools for the first time (before, they had relied on state funding almost exclusively). Funding for school construction, extra teachers, aid to low income schools, free and reduced lunch programs were all a part of this act, which we still see affecting the schools today.
His second effort was the Higher Education Act of 1965, which created a large federal financial aid program to offer low-interest loans and scholarships to needy students. This has been periodically reauthorized by Congress again and again, most recently in 2008.
So in terms of lasting effects, I'd say LBJ was the most recent education President.
Since Texas has not had a president of its own since it joined the US, I assume that you are talking about US presidents who come from Texas. If that is the case, I would say that both Lyndon Johnson (1963-1969) and George W. Bush (2001-2009) were concerned with education.
Johnson was concerned with education as part of his War on Poverty and Great Society programs. Bush was concerned with what he saw as bad results for American schools all across the board. He was the main force behind the passing of the No Child Left Behind law that is still in force today.
The development of educational quality has been contentious with Texas politicians since reconstruction.
As much as only Nixon could have gone to China, only Lyndon Johnson could have enacted Federal legislation, through The War on Poverty, that established the legal right of educational quality for all students. Subsequent Presidents were impelled to initiate Federal legislation that began to build academic educational quality upon that foundation (Addressing various issues through IDEA, NCLB, and Title I regulations which increasingly tied Federal money to factors such as student performance on testing of minimal academic standards).
Interestingly enough, Lyndon Johnson began his work life as a teacher in Texas public schools.