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Overview
There are two basic ways to play a demonologist, a warrior mage demonologist and a summoner demonologist. It is also possible to play a demonologist like a normal swordmaster.
Warrior mage demonologist
A warrior mage demonologist is a swordmaster that wields a demonblade and uses its spells to enhance his deadliness.
Demon Blade is your basic spell that makes your melee a lot more powerful against many monsters. You should keep it running pretty much constantly.
Demon Field is a handy spell to use whenever you get surrounded by lots of weak monsters. Cast it the first thing in the battle and let it do its helpful work while you fight. Not only lice die quickly, but even moderately strong monsters gradually perish. The spell has a very large radius, it lasts a long time, and few monsters resist nexus.
Summoner demonologist
A summoner demologist uses the demonhorn to summon pet demons to his aid.
The idea is to build a powerful, preferentially chainsummoning demon army. As might be expected, Pit Fiends are much more to be desired than Vrocks, even if they are both levelled to the same number. Good luck helps you get better demons.
Combining the styles
The tricky part about combining the styles is that at level 45 the Demon Blade spell starts to do splash damage. If you want to have both the extra melee damage and pets, you need to either be extremely careful which monster you hit, or leave your demonology to 44 and overall less powerful.
The Gothmog set suits well a warrior mage demonologist but a summoner demonologist's effectiveness will suffer because the massive minus to luck will result on average in lower level demons than otherwise would be the case.
Sometimes it is necessary to change styles temporarily. For example, if a warrior mage demonologist gets a princess quest for something like bronze golems, or several skull druj in an open room, it may not be viable to just charge in and get swamped in nasty summons. If antisummoning corridors are not possible due to the quest monster being never-moving or the sort of dungeon layout that allows balrogs being summoned before the corridor may be put into action, it may be a good idea to use an "anti-summoning field" of a large number of pet demons. Monsters cannot summon where another monster already is. Expect quest monsters get summons through in the sidelines of your horde, but the effect will be much less deadly, and you will be able to move in relative safety through your pets and lay the final blow on the quest monsters.
Swordmaster demonologist
So you found a *thanc in the Barrow-downs? No problem. House your demonblade and play a swordmaster. You may later switch to playing a demonology-using demonologist if you wish.