Go to the admin and there you'll the configuration for email sending. "Global Settings" --> "Email Settings". You should definitely avoid the phpmail method. While it is easy and convenient, it is also very often blocked and associated with spamming, because anyone can send mass emails this way via php, faking others email addresses, etc.
You need to have a good smtp account, not something like hotmail, yahoo, etc. There is also an article at the blog of Limesurvey Consulting (
www.limesurvey-consulting.com/how-to-pre...ing-treated-as-spam/
) explaining the basic principals to avoid being marked as spam. If you search here in the forum, I have written a few things as well.
Some hosts configure their emails servers very badly, which means you can quickly be marked as spam. This is a science on it's own and has little to do with Limesurvey. This is more a general problem of sending emails, especially in bigger quantities and to people you might not know personally.