Anytime! With Medi-Share there is no open enrollment period, so you can enroll anytime. Coverage begins the first of the month.
One thing to keep in mind is that since Medi-Share has no open enrollment period, the deductible (or AHP as Medi-Share calls it) resets based on a rolling 12-month period from the date at which you sign up (rather than a calendar year rest of Jan 1). Learn more about Medi-Share here.