They can only wear orders they have. So, Edward and William don't have a 'neck decoration' to wear in addition to the more important (categories of the) orders they are already wearing. For example, the one Harry is wearing is a Spanish order he received during the Spanish state visit for being the host/tour guide at Westminster Abbey for the Spanish king and queen. Anne and Andrew received similar orders at that time for hosting other activities.
Edit: Mbruno is right, he is wearing the Knight Commander-decoration of the RVO instead; the Order of Isabella has a white/yellow band and a different cross.
I edited my answer since I had not at first noticed that Maria-Olivia was asking about the St Paul's service and not about their uniforms at the Queen's Birthday parade.
But I am still confused about all the princes wearing their stars (for example of the Garter or the RVO) and necklace insignia (when they have it) with morning suit. Normally one would only wear a miniature badge on the lapel with that kind of attire. Is it because it was a special occasion?
I think Prince Edward could have worn his GCVO badge at his neck. Prince Michael did, and the Duke of Kent wore his GCMG badge the same way. I think the only badges, normally worn on a sash, that can never be worn around the neck are for the Garter and Thistle.
Yes, that is right. So Prince William was the only one who didn't have necklace insignia to wear !
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