I think you can apply to the Career Start program but not the College Program. I know I read somewhere that colleges courses taken while in high school (dual credit) don't qualify. Also, you need to be enrolled in college and have completed at least one semester. From the College Program website:
What are the application requirements?
To apply, students must be enrolled currently in a college or university and have completed at least one semester. Candidates must be at least 18 years old and meet his or her school's requirements for participation.
However, you can apply during your first semester to do the program the next semester as long as you're at least 18.