Confused about timing, enrollment, and tests

[LERE]

Hi all! I'm new here and although I've found a great deal of information, I'm still confused about a couple things:

1) If I want to test out most of my degree at one of the Big 3, do I have to enroll there before taking any CLEP/DSST test? Or, if I start taking some tests now and then enroll with them, will they take those tests into account?

2) Once enrolled, does it matter in which order I take the tests? For example, can I take something like CLEP Management first (a professional business requirement) and then CLEP Humanities (a general education requirement)?

Thanks in advance!