Some of the different types of solvents you can keep around are Micro Set, Micro Sol, and Solvaset. These are in order of potency, Micro set being the mildest, Solvaset being the strongest. Use Microset as a "wetting" agent, just brush it on the model, then place the decal as you normally would. After you given this time to dry, usually over night, you can then go over it with Micro Sol if it hasn't snugged down all the way or if you have some air bubbles just poke a small hole in the bubble with an xacto knife and put the solvent on. Micro Set and Micro Sol seem to work well with most kit and after market decals. Solvaset is totally different. I have actually had it melt Monogram and Hasegawa decals and only use it as a last resort and ALWAYS check it on a decal I won't be using. If you notice most reviews in FSM have a statement in them saying " Decals respond well to" whatever. Plus many aftermarket decals will recommend solvents.
As for getting old decals off this can be tricky. I have used plain old packing tape to pull them off. Just put the tape over the decal, rub it down and hope for the best. I haven't had any problem pulling paint off but it is something to be concerned about. If you just need to get one decal off and go over it with basically the same thing this seems to work well for me. I have tried to soft with the solvent but then I just ended up with a gooey mess.
Hope this helps you out.
Wayners
Go Eagles! 334th Fighter Squadron
Me and my F-4E
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