Not only the line of succession was against Aemond and his desire for the throne, but also ancient traditions of his house. Firstborn getting everything, of course. Especially given that the first son was Aegon, older brother Aemond always saw as unworthy and disgraceful. And Aegon getting everything was infuriating, specially when what Aegon got was you marrying him, not Aemond.
Marriage with Prince Aegon was not filled with love or affection, only created for duty surely. While Aemond watched from the sidelines as Aegon neglected you, neglected his duties, denied you the love you deserve. One-eyed prince wanted you, craved to give you affection you deserved. If he was given the chance to marry you, he would do that on instant, and not only for the sake of duty.
Even from your childhood, even before the betrothal between you and Aegon was announced, Aemond saw you for who you are, cherished every moment in your presence. And as both you grew up his feelings only intensified. He wanted to protect you, shield you from your husband and the world itself, give you the care and support he knew you wanted and never got. The always reserved and composed prince would be emotional, but only for you. For him - you were and are the most precious and fragile thing in the world.
But what could be done? Your marriage with his older brother was preventing him from making any open statements, undoubtedly. Aemond’s stoic and cold demeanor stopped him from reaching out to you, from showing you the real extent of his desire and feelings. Yet his presence was noticeable. Even with always remaining nonchalant and closed off, Prince would be near you, his quiet presence would be there, near you. Near the one he wanted the most, yet could never get.