Biometric card is not something separate to application procedure. It is part of application.  Not all categories can apply for PEO services. I suggest you read the relevant application form and UKBA website first, and then ask if anything is unclear.

Hello there,
I will be applying for ILR in next few months and I have few questions as follow.

Can anyone choose to apply through PEO service instead of Postal Service? If decision is made in the same day then it's the better way for sure.

How early can we have biometric test prior to ILR application? Does it work if I apply for biometrics card now and apply after 3 months.

I would really appreciate your replies.
Thanks