Gains on this engine are small yet there is plenty to do as I did a fair bit of work on my one.
280mm Front brake setup
4-2-1 Manifold
Cold air intake to standard box
Green cotton filter (standard shape)
Smooth air box
Blank out breather to air box
Breather filter (can't member size sorry)
Uprated exhuast (Sport exhuast)
De-cat
Port polished
Change sump to the anti foam one (euro shop/part can't find a seller in the uk for these, don't know why)
Coilovers (a must this thing can easily be put on 2 wheels)
G40 Injectors (think they work with the standard loom without modification)
Re-map with all that like an extra 15bhp max
But if you want to go abit more of a push there's a few easy options, such as cams, you can get aggressive cam's with a maximum of no more than 270degrees before you start to do damage. Shrick do a 268degree cam which would be perfect, but it depends how much of a daily drive this car is. If it is a daily car you can re-use another cam from another VW engine, its a 3F cam with 219 degree's so it won't cause discomfort, cannot remember what it came off, think it was off the 1.6 mk3 polo's and golfs, dig around its commonly known as a 3F cam, due to the letters 3F stated on the cam somewhere.
You can uprate the throttle body to off a N/A 20VT engine, again don't quote me which 20VT engine, but a flange is involved to make it fit correctlt, but the throttle cable link is on the correct side (and the plug is identical to the polo one). But this can seem abit pointless due to the need of a new air box and restricitons in the diameter of the actual intake manifold.
Then there is a turbo route, depending how well you are at welding, the standard pistons on the 6n polo can with stand 0.6 bar (8.7psi) of boost max, so if you handy with a welder you could pick up an old mini 1.3 low boost turbo and make the turbo side completely mechanically adjusted to react accordingly with the aid of a atmospheric dump valve. Low boost setups can see around 110BHP I believe.
However there is the whole compression ratio business, a common thing some people do is breed two of the engines together, such as top half 1.6 8v SOHC (AEE) petrol engine which has bigger valves and bore channels, whilst the bottom end and pistons are off the AEX 1.4 engine, can't remember what engine that is as I no longer have a polo or the Hynes for it, but if memory serves me well it was practically a similar if not idnetical to the APQ engine, but don't quote. This would drop the compression down considerably (from 10.2:1 too around 8.6:1), but if you do go this way, remember forged pistons as then you can break the low boost barrier and start talking more like 200bhp with a G40 ECU and a k03. There are companies that actually do a bolt on manifold for a k03 turbo to the standard polo, think they where "SLS" and "Rothe". If you do build this engine rmember due to the low compression it won't run very well as a NA engine. Other issue is the polo's standard ECU does not have a MAP sensor (or it does but it's only good upto 0.4bar), so people tend to swap for a g40 ecu.... or the lazy guys get a g40 engine to begin with as a conversion rather than complicating things with engineering know how.
Some other guys go down a slightly differernt route and use bike carbs followed by a custom inlet manifold, with the use of 2 or 4 carbs. A guy I once met had 125bhp on the carb set up on the 1.4 8v engine. Again some guys go down this route with a turbo system as well.
Dunno how else I can help you, I know the engines on the mk4 were not to different from the mk3 golf engines, so some engine parts can be sourced from golfs, think the 1.6 engine was identical even down to engine code.It's been a long time since I was into polo's I had two mk4 (6n1), got bored of them, but I always still think about having one maybe as a trackday project, better yet pick up an older Seat Ibiza mk2 (6k) or even the 1.8T Ibiza's (mk3 6k2) with a strip out and some engine work its weight to power can be effective, but on the polo mk4 a 1.8T engine is a very tight fit.