One solution would be to have different skills require different amounts of work to get to 100% proficiency. When some skills max out very quickly, then it won't take very long until the first merger options become available.
This of course puts a limit on how far certain skills can be developed. How committed are you to the idea that a skill must be maxed out before it unlocks a merged skill? You could already enable certain skill mergers on earlier proficiency. For example, a character would already gain the option to learn Sticky Fireball with Fireball 30% and Stick Ball 40%.
If you do want to stay committed to the idea that mergers may only happen when a skill is maxed out, want mergers to happen early but also want to give the option to invest a lot of effort into mastering the art of fireballing, then you could solve that by also unlocking a more advanced version of a skill when it's maxed out. For example, when the character reached 100% proficiency in Fireball, they don't just unlock the merger with Stick Ball, but also unlock a new skill "Greater Fireball". Greater Fireball is basically just a stronger version of Fireball which also requires a lot more effort to bring to 100% proficiency.
That would mean that raising a skill to 100% gives two different progression options: diversification (by investing in a merged skill) or specialization (by investing in an advanced version of the same skill).