It's difficult to answer the question the way you phrased it. Passing a CLEP demonstrates knowledge commensurate with that of a college student who has recently completed a course in that subject area. The exams are developed and scaled so that college students who recently scored a C in the course will typically score a 50 on the CLEP exam. With a little research on the web, you can find a lot more detail, but that's the basics of it.
Having said that, whether you will learn as much as you would in a class depends on you, your learning style, your study materials, the class you might have taken, its instructor, and plenty of other factors. Many college courses have excellent instructors and provide an excellent learning experience. And many have lousy, inexperienced, unmotivated instructors, and are a big waste of time.
Personally, I've never regretted taking an exam instead of a course. Like Mark Twain, I've never let my schooling interfere with my education.
-Gary-